Light-induced conical intersections(LICIs)present a distinctive mechanism for nonadiabatic coupling,thereby facilitating ultrafast chemical reactions,including the indirect photodissociation of diatomic molecules.In c...Light-induced conical intersections(LICIs)present a distinctive mechanism for nonadiabatic coupling,thereby facilitating ultrafast chemical reactions,including the indirect photodissociation of diatomic molecules.In contrast to static conical intersections,LICIs are dynamically tunable,providing a pathway for precise control of molecular dissociation.In this study,we employ the time-dependent quantum wave packet method to investigate the dissociation dynamics of the OH molecule,focusing on its ground state X^(2)Πand repulsive state 1^(2)Σ~-.By varying laser field parameters(intensity,full width at half maximum(FWHM),and wavelength),we elucidate how nonadiabatic coupling governs selective dissociation channel control.Our findings reveal that the choice of initial vibrational states and the tailoring of laser conditions significantly influence dissociation pathways,providing theoretical insights into manipulating molecular dynamics via LICIs.These results provide a foundation for future experimental studies and the development of advanced molecular control techniques.展开更多
The ultrafast dynamics through conical intersections in 2,6-dimethylpyridine has been studied by femtosecond time-resolved photoelectron imaging coupled with time-resolved mass spectroscopy. Upon absorption of 266 nm ...The ultrafast dynamics through conical intersections in 2,6-dimethylpyridine has been studied by femtosecond time-resolved photoelectron imaging coupled with time-resolved mass spectroscopy. Upon absorption of 266 nm pump laser, 2,6-dimethylpyridine is excited to the S2 state with a ππ character from So state. The time evolution of the parent ion signals consists of two exponential decays. One is a fast component on a timescale of 635 fs and the other is a slow component with a timescale of 4.37 ps. Time-dependent photo- electron angular distributions and energy-resolved photoelectron spectroscopy are extracted from time-resolved photoelectron imaging and provide the evolutive information of S2 state. In brief, the ultrafast component is a population transfer from S2 to S1 through the S2/S1 conical intersections, the slow component is attributed to simultaneous IC from the S2 state and the higher vibrational levels of S1 state to So state, which involves the coupling of S2/S0 and S1/So conical intersections. Additionally, the observed ultrafast S2--＋S1 transition occurs only with an 18% branching ratio.展开更多
The effect of conical intersection on the excited dynamics of benzene is studied by ab initio theory of electronic structure,which provides an important insight into photophysical and photochemical reactions.Based on ...The effect of conical intersection on the excited dynamics of benzene is studied by ab initio theory of electronic structure,which provides an important insight into photophysical and photochemical reactions.Based on the CASSCF(6,6)/6-31+G(d,p)method,the topological structures of conical intersections S_(1)/S and S_(2)/S_(1)of benzene,as well as the optimal structures of the ground state(S)and excited states(S_(1),S_(2)),are determined.The energy minima of the S_(1)state and S_(2)state are estimated at 4.608 e V and 6.889 e V,respectively.In addition,the energy values of the conical intersections of S_(1)/S and S_(2)/S_(1)are predicted to be 5.600 e V and 6.774 e V.According to the topological structures and energy values of the S_(2)/S_(1)and S_(1)/S conical intersections,the photophysical behavior of benzene excited to the S_(2)state and the effects of the S_(2)/S_(1)and S_(1)/S conical intersections are discussed in detail.展开更多
Within the Born-Oppenheimer(BO)approximation,nuclear motions of a molecule are often envisioned to occur on an adiabatic potential energy surface(PES).However,this single PES picture should be reconsidered if a conica...Within the Born-Oppenheimer(BO)approximation,nuclear motions of a molecule are often envisioned to occur on an adiabatic potential energy surface(PES).However,this single PES picture should be reconsidered if a conical intersection(CI)is present,although the energy is well below the CI.The presence of the CI results in two additional terms in the nuclear Hamiltonian in the adiabatic presentation,i.e.,the diagonal BO correction(DBOC)and the geometric phase(GP),which are divergent at the CI.At the same time,there are cusps in the adiabatic PESs.Thus usually it is regarded that there is numerical difficulty in a quantum dynamics calculation for treating CI in the adiabatic representation.A popular numerical method in nuclear quantum dynamics calculations is the Sinc discrete variable representation(DVR)method.We examine the numerical accuracy of the Sinc DVR method for solving the Schrodinger equation of a two dimensional model of two electronic states with a CI in both the adiabatic and diabatic representation.The results suggest that the Sinc DVR method is capable of giving reliable results in the adiabatic representation with usual density of the grid points,without special treatment of the divergence of the DBOC and the GP.The numerical uncertainty is not worse than that after the introduction of an arbitrary vector potential for accounting the GP,whose accurate form usually is not easy to obtain.展开更多
Aggregation-induced emission luminogens(AIEgens)exhibit viscosity-responsive behavior resembling those of molecular rotors;however,their response mechanisms are more complex and cannot be adequately described using si...Aggregation-induced emission luminogens(AIEgens)exhibit viscosity-responsive behavior resembling those of molecular rotors;however,their response mechanisms are more complex and cannot be adequately described using simple rotational models.AIEgens demonstrate intricate dynamics that are highly dependent on their molecular structures.In this study,we synthesized water-soluble derivatives of representative AIEgens,including tetraphenylethene(TPE),bis(N,N-dialkylamino)anthracene(BDAA),and bridged stilbene,and systematically investigated the dependence of their photophysical properties in water/glycerol mixed solvents on temperature and viscosity.To elucidate the origin of their viscosity responsiveness,quantum chemical calculations were conducted to analyze their potential energy surfaces(PESs).The results revealed that compared to typical molecular rotors,these AIEgens exhibit significantly higher sensitivity to viscosity in low-viscosity regions.Notably,for TPE and BDAA derivatives,the viscosity responsiveness was found to be governed not by the activation energy barrier(ΔE_(a))based on the PES,but rather by the viscosity-dependent constraints on molecular structural changes.Furthermore,molecules possessing multiple aromatic rings or large,flexible,rotatable moieties were found to exhibit enhanced sensitivity to viscosity due to increased frictional interactions in solutions.This study provides critical insights into the mechanistic origins of the viscosity responsiveness of AIEgens,thereby advancing the fundamental understanding of their behavior and expanding their potential application as viscositysensitive probes.展开更多
We constructed a new set of diabatic poten-tial energy surfaces(PESs)for the two low-est states involved in Li+Li_(2)reaction by us-ing the fundamental-invariant neural net-work method.The Li_(3)system exhibits a coni...We constructed a new set of diabatic poten-tial energy surfaces(PESs)for the two low-est states involved in Li+Li_(2)reaction by us-ing the fundamental-invariant neural net-work method.The Li_(3)system exhibits a coni-cal intersection(CI)at the geometric D_(3)h symmetries with the energy of the CI point significantly lower than the ground-state en-ab initio ergy of the diatomic molecule.The diabaitc PESs accurately reproduce adiabatic en-ergies,derivative coupling,and energy gradient information,thereby providing a high-fideli-ty description of the CI between the two lowest electronic states.Quantum dynamical calcu-lations have revealed significant non-adiabatic effects in the Li+Li_(2)reaction.展开更多
A new two-state diabatic potential energy matrix(DPEM)for H3 has been constructed,based on the fun-damental invariant neural network(FI-NN)diabatization method pro-posed in our previous work[Phys.Chem.Chem.Phys.21,150...A new two-state diabatic potential energy matrix(DPEM)for H3 has been constructed,based on the fun-damental invariant neural network(FI-NN)diabatization method pro-posed in our previous work[Phys.Chem.Chem.Phys.21,15040(2019)].In that initial effort,a two-state DPEM was constructed only with a 10 eV energy threshold.The current work aims to expand the en-ergy range and improve the accura-cy of DPEM.This is achieved by the utilization of full configuration inter-action(FCI)with aug-cc-pVnZ ba-sis sets and complete basis set(CBS)extrapolation.The original dataset is augmented with additional points with higher adiabatic energies,which give rise to a total of 10985 data points.The DPEM constructed in this work now enables accurate representation of adiabatic energies up to 18 eV.Quantum dynamic calculations based on this DPEM are nearly identical to those obtained from benchmark surfaces,which makes it the most accurate DPEM for the H3 system to date,therefore facilitating detailed exploration of reaction mechanisms at higher collision energies.展开更多
The decay dynamics of N, N-dimethylthioacetamide after excitation to the S3（ππ＊） state was studied by using the resonance Raman spectroscopy and complete active space self- consistent field method calculations. T...The decay dynamics of N, N-dimethylthioacetamide after excitation to the S3（ππ＊） state was studied by using the resonance Raman spectroscopy and complete active space self- consistent field method calculations. The UV-absorption and vibrational spectra were as- signed. The A-band resonance Raman spectra were obtained in acetonitrile, methanol and water with the laser excitation wavelengths in resonance with the first intense absorption band to probe the Franck-Condon region structural dynamics. The CASSCF calculations were carried out to determine the excitation energies and optimized structures of the lower- lying singlet states and conical intersection point. The A-band structural dynamics and the corresponding decay mechanism were obtained by the analysis of the resonance Raman in- tensity pattern and the CASSCF calculated structural parameters. The major decay channel of S3,FC （ππ＊）→S3（ππ＊）/S1 （nπ＊）→S1（nπ＊） is proposed.展开更多
Herein we have employed high-level multi-reference CASSCF and MS-CASPT2 electronic structure methods to systematically study the photochemical mechanism of intramolecularly hydrogen-bonded 2-（2＇-hydroxyphenyl）-4-me...Herein we have employed high-level multi-reference CASSCF and MS-CASPT2 electronic structure methods to systematically study the photochemical mechanism of intramolecularly hydrogen-bonded 2-（2＇-hydroxyphenyl）-4-methyloxazole. At the CASSCF level, we have optimized minima, conical intersections, minimum-energy reaction paths relevant to the excited-state intramolecular proton transfer （ESIPT）, rotation, photoisomerization, and the excited-state deactivation pathways. The energies of all structures and paths are refined by the MS-CASPT2 method. On the basis of the present results, we found that the ESIPT process in a conformer with the OH... N hydrogen bond is essentially barrierless process; whereas, the ESIPT process is inhibited in the other conformer with the OH... O hydrogen bond. The central single-bond rotation of the S1 enol species is energetically unfavorable due to a large barrier. In addition, the excited-state deactivation of the S1 keto species, as a result of the ultrafast ESIPT, is very efficient because of the existence of two easily-approached keto S1/S0 conical intersections. In stark contrast to the S1 keto species, the decay of the S1 enol species is almostly blocked. The present theoretical study contributes valuable knowledge to the understanding of photochemistry of similar intramolecularly hydrogen-bonded molecular and biological systems.展开更多
The photophysics of 3-dimethylamino-2-methyl-propenal （DMAMP） after excitation to the S2 （ππ^＊） electronic state was studied using the resonance Raman spectroscopy and complete active space self-consistent fiel...The photophysics of 3-dimethylamino-2-methyl-propenal （DMAMP） after excitation to the S2 （ππ^＊） electronic state was studied using the resonance Raman spectroscopy and complete active space self-consistent field method calculations. The transition barriers of the ground state tautomerization reactions between DMAMP and its three isomers were determined at B3LYP/6-311＋＋G（d,p） level of theory. The vibrational spectra were assigned. The A- band resonance Raman spectra were obtained in acetonitrile with excitation wavelengths in resonance with the first intense absorption band to probe the structural dynamics of DMAMP. The B3LYP-TD computation was carried out to determine the relative A-band resonance Raman intensities of the fundamental modes, and the result indicated that the vibronic-coupling existed in Franck-Condon region. Complete active space self-consistent field （CASSCF） calculations were carried out to determine the excitation energies of the lower-lying singlet and triplet excited states, the conical intersection points and the intersystem crossing points. The A-band short-time structural dynamics and the corresponding decay dynamics of DMAMP were obtained by analysis of the resonance Raman intensity pattern and CASSCF computations. It was found that a sudden de-conjugation between C1=O6 and C2=C3 occurred at the Franck-Condon region of the S2（ππ^＊） state, while the enhancement of the conjugation interaction between C3 and N（CH3）2, and between C1 and C2 evolutions shortly after the wavepacket leaves away the Pranck-Condon region via the excited state charge redistribution. The de-conjugation interaction between C1=O6 and C2=C3 made the rotation of C3=N（CH3）2 group around the C2-C3 bond much easier, while the enhanced conjugation between C1 and C2, and between C3 and N（CH3）2 made the rotation around the C1-C2 bond and C3-N5 more difficult. It was revealed that the initial structural dynamics of DMAMP was predominantly towards the CI-I（S2/S0） point, while the opportunities towards either CI-2（S2/S0） or CI-3（S2/S0） point were negligible. Two decay channels of DMAMP from S2,FC（ππ^＊） to So or Tl,min via various CIs and ISCs were proposed.展开更多
We report that the photoinduced dynamics of the phytochrome chromophore is strongly dependent on the protonation/deprotonation states of the pyrrole ring. The on-the-fly surface hopping dynamics simulations were perfo...We report that the photoinduced dynamics of the phytochrome chromophore is strongly dependent on the protonation/deprotonation states of the pyrrole ring. The on-the-fly surface hopping dynamics simulations were performed to study the photoisomerization of different protonation/deprotonation phytochrome chromophore models. The simulation results indicate that the deprotonations at the pyrrole rings significantly modify the photoinduced nonadiabatic dynamics, leading to distinctive population decay dynamics and different reaction channels. Such feature can be well explained by the formation of the different hydrogen bond network patterns. Therefore, the proper understanding of the photoisomerization mechanism of phytochrome chromophore must take the hydrogen bond network into account. This work provides the new insights into the photobiological functions of phytochrome chromophore and suggests the possible ideas to control of its photoconversion processes for further rational engineering in optical applications.展开更多
Full-dimensional adiabatic potential energy surfaces of the electronic ground state X and nine excited states A,I,B,C,D,D',D'',E' and F of H_(2)O molecule are developed at the level of internally contr...Full-dimensional adiabatic potential energy surfaces of the electronic ground state X and nine excited states A,I,B,C,D,D',D'',E' and F of H_(2)O molecule are developed at the level of internally contracted multireference configuration interaction with the Davidson correction.The potential energy surfaces are fitted by using Gaussian process regression combining permutation invariant polynomials.With a large selected active space and extra diffuse basis set to describe these Rydberg states,the calculated vertical excited energies and equilibrium geometries are in good agreement with the previous theoretical and experimental values.Compared with the well-investigated photodissociation of the first three low-lying states,both theoretical and experimental studies on higher states are still limited.In this work,we focus on all the three channels of the highly excited state,which are directly involved in the vacuum ultraviolet photodissociation of water.In particular,some conical intersections of D-E',E'-F,A-I and I-C states are clearly illustrated for the first time based on the newly developed potential energy surfaces(PESs).The nonadiabatic dissociation pathways for these excited states are discussed in detail,which may shed light on the photodissociation mechanisms for these highly excited states.展开更多
The nonadiabatic dynamics of methyl nitrate(CH_(3)ONO_(2))is studied with the on-the-fy trajectory surface hopping dynamics at the ADC(2)level.The results confirmed the existence of the ultrafast nonadiabatic decay to...The nonadiabatic dynamics of methyl nitrate(CH_(3)ONO_(2))is studied with the on-the-fy trajectory surface hopping dynamics at the ADC(2)level.The results confirmed the existence of the ultrafast nonadiabatic decay to the electronic ground state.When the dynamics starts from S_(1) and S_(2),the photoproducts are CH_(3)O+NO_(2),consistent with previous results obtained from the experimental studies and theoretical dynamics simulations at more accurate XMS-CASPT2 level.The photolysis products are CH_(3)O+NO_(2) at the ADC(2)level when the dynamics starts from S3,while different photolysis products were obtained in previous experimental and theoretical works.These results demonstrate that the ADC(2)method may still be useful for treating the photolysis mechanism of CH_(3)ONO_(2) at the long-wavelength UV excitation,while great caution should be paid due to its inaccurate performance in the description of the photolysis dynamics at the short-wavelength UV excitation.This gives valuable information to access the accuracy when other alkyl nitrates are treated at the ADC(2)level.展开更多
Herein we have employed the MS-CASPT2//CASSCF method to study the S1 excited-state intramolecular proton transfers （ESIPTs） of recently synthesized ortho-hydroxyl GFP core chromophores, i.e. OHIM, CHBDI, and MHBID, ...Herein we have employed the MS-CASPT2//CASSCF method to study the S1 excited-state intramolecular proton transfers （ESIPTs） of recently synthesized ortho-hydroxyl GFP core chromophores, i.e. OHIM, CHBDI, and MHBID, and their excited-state relaxation pathways. We have found that in OHIM and CHBDI, the ESIPT process is associated with small barriers of 3.4 and 4.2 kcal/mol; while, in MHBDI, it becomes essentially barrierless. Moreover, we have found two main S1 excited-state radiationless channels. In the first one, the enol S1 species decays to the So state via the enol S1/S0 conical intersection after overcoming considerable barriers of 7.0 and 7.7 kcal/mol in OHIM and CHBDI （however, in MHBDI, it is nearly barrierless）. In the second one, the keto S] species is first generated through the ESIPT event; then, it is de-excited into the So state in the vicinity of the keto S1/S0 conical intersection. These energetically allowed excited-state decay channels rationalize ex- perimentally observed ultralow fluorescence quantum yields. The insights gained from the present work may help to guide the design of new ortho-hydroxyl GFP core chromophores with improved fluorescence emission and brightness.展开更多
Aggregation-induced emission luminogens(AIEgens)are typically largeπ-conjugated molecules,but their low affinity and noninvasiveness toward analytes limit practical applications.To address this,smaller,more planar AI...Aggregation-induced emission luminogens(AIEgens)are typically largeπ-conjugated molecules,but their low affinity and noninvasiveness toward analytes limit practical applications.To address this,smaller,more planar AIEgens are needed.Stilbene,though structurally suitable,lacks visible luminescence.Here,we report a minimally modified stilbene-based AIEgen-4-dipropylamino-4'-cyano-bridged stilbene(DpCBS[7])-that exhibits fluorescence solvatochromism and efficient AIE across a broad polarity range in the visible region.DpCBS[7]exhibits low quantum yields(Φ_(fl)=0.010.04)in solvents from nonpolar n-hexane to polar dimethyl sulfoxide,with large Stokes shifts,viscosity-sensitive luminescence,and highly efficient solid-state luminescence(Φ_(fl)=0.70).To elucidate its dual solvatochromic and AiE behavior,femtosecond transient absorption spectroscopy was conducted.In solution,DpCBS[7]displays transient absorption with lifetimes of 21 ps(toluene)and 56 ps(acetonitrile)at 293 K,indicating ultrafast nonradiative decay leading to low Φ_(fl).Arrhenius analysis over the temperature range of 263-313 K revealed activation energies(ΔE_(a))of 9.90kJ/mol in toluene and 12.8 kJ/mol in acetonitrile for the S_(1)→S_(0) decay of DpCBS[7].The ΔE_(a) values show no clear systematic dependence on solvent polarity.In contrast,pre-exponential factor A remains consistently high regardless of solvent polarity,indicating that the striking photophysical response is governed primarily by the pre-exponential factor rather than by modulation of the activation energy.These findings highlight the fundamental importance of tailoring the distribution function through structural modification as a robust strategy to control AiE characteristics.展开更多
We computationally investigated the molecular aggregation effects on the excited state deactivation processes by considering both the direct vibrational relaxation and the S0/S1 surface crossing,that is,the minimum en...We computationally investigated the molecular aggregation effects on the excited state deactivation processes by considering both the direct vibrational relaxation and the S0/S1 surface crossing,that is,the minimum energy conical intersection(MECI).Taking classical AIEgens bis(piperidyl)anthracenes(BPAs)isomers and the substituted silole derivatives as examples,we show that the deformation ofMECI always occurs at the atom with greater hole/electron overlap.Besides,the energetic and structural changes of MECI caused by substituent has been investigated.We find that effective substituent such as the addition of the electron-donating groups,which can polarize the distribution of hole/electron density of molecules,will lead to the pyramidalization deformation of MECI occurring at the substituent position and simultaneously reduce the required energy to reach MECI.And MECI is sterically restricted by the surrounding molecules in solid phase,which remarkably hinders the non-radiative decay through surface crossing.Through quantitative computational assessments of the fluorescence quantum efficiency for both solution and solid phases,we elucidate the role of MECI and its dependence on the substitutions through pyramidalization deformation,which give rise to the aggregation-induced emission(AIE)phenomenon for 9,10-BPA,to aggregation-enhance emission(AEE)behavior for 1,4-BPA,and to conventional aggregation-caused quenching(ACQ)for 1,5-BPA.We further verify such mechanism for siloles,for which we found that the substitutions do not change the AIE behavior.Our findings render a general molecular design approach to manipulating the aggregation effect for optical emission.展开更多
When femtosecond （fs） timeresolved experiments are used to study ultrafast processes, quantum beat phenomena are often observed. In this paper, to analyze the fs timeresolved spectra, we will present the density mat...When femtosecond （fs） timeresolved experiments are used to study ultrafast processes, quantum beat phenomena are often observed. In this paper, to analyze the fs timeresolved spectra, we will present the density matrix method, a powerful theoretical technique, which describes the dynamics of population and coherence of the system. How to employ it to study the pumpprobe experiments and fs ultrafast processes is described. The transition of pyrazine is used as an example to demonstrate the application of the density matrix method. Recently, Suzuki＇s group have employed the 22 fs time resolution laser to study the dynamics of the state of pyrazine. In this case, conical intersection is commonly believed to play an important role in this nonadiabatic process. How to treat the effect of conical intersection on nonadiabatic processes and fs timeresolved spectra is presented. Another important ultrafast process, vibrational relaxation, which takes place in subps and ps range and has never been carefully studied, is treated in this paper. The vibrational relaxation in water dimer is chosen to demonstrate the calculation. It should be noted that the vibrational relaxation of （H20）2 has not been experimentally studied but it can be accomplished by the pump-probe experiments.展开更多
基金supported by the National Natural Science Foundation of China(Grant Nos.12134005 and 12334011)the Major Research Plan of the National Natural Science Foundation of China(Grant No.92461301)。
文摘Light-induced conical intersections(LICIs)present a distinctive mechanism for nonadiabatic coupling,thereby facilitating ultrafast chemical reactions,including the indirect photodissociation of diatomic molecules.In contrast to static conical intersections,LICIs are dynamically tunable,providing a pathway for precise control of molecular dissociation.In this study,we employ the time-dependent quantum wave packet method to investigate the dissociation dynamics of the OH molecule,focusing on its ground state X^(2)Πand repulsive state 1^(2)Σ~-.By varying laser field parameters(intensity,full width at half maximum(FWHM),and wavelength),we elucidate how nonadiabatic coupling governs selective dissociation channel control.Our findings reveal that the choice of initial vibrational states and the tailoring of laser conditions significantly influence dissociation pathways,providing theoretical insights into manipulating molecular dynamics via LICIs.These results provide a foundation for future experimental studies and the development of advanced molecular control techniques.
基金This work was supported by the National Natural Science Foundation of China （No.10704083）,the Innovation Foundation of Chinese Academyof Sciences （No.KJCX1-YW-N30）, and the Public Science and Technology Program of Shenzhen （No.SY200806260026A）.
文摘The ultrafast dynamics through conical intersections in 2,6-dimethylpyridine has been studied by femtosecond time-resolved photoelectron imaging coupled with time-resolved mass spectroscopy. Upon absorption of 266 nm pump laser, 2,6-dimethylpyridine is excited to the S2 state with a ππ character from So state. The time evolution of the parent ion signals consists of two exponential decays. One is a fast component on a timescale of 635 fs and the other is a slow component with a timescale of 4.37 ps. Time-dependent photo- electron angular distributions and energy-resolved photoelectron spectroscopy are extracted from time-resolved photoelectron imaging and provide the evolutive information of S2 state. In brief, the ultrafast component is a population transfer from S2 to S1 through the S2/S1 conical intersections, the slow component is attributed to simultaneous IC from the S2 state and the higher vibrational levels of S1 state to So state, which involves the coupling of S2/S0 and S1/So conical intersections. Additionally, the observed ultrafast S2--＋S1 transition occurs only with an 18% branching ratio.
基金supported by the National Key Research and Development Program of China(Grant No.2019YFA0307700)the National Natural Science Foundation of China(Grant Nos.11974381,11674355,and 21773299)。
文摘The effect of conical intersection on the excited dynamics of benzene is studied by ab initio theory of electronic structure,which provides an important insight into photophysical and photochemical reactions.Based on the CASSCF(6,6)/6-31+G(d,p)method,the topological structures of conical intersections S_(1)/S and S_(2)/S_(1)of benzene,as well as the optimal structures of the ground state(S)and excited states(S_(1),S_(2)),are determined.The energy minima of the S_(1)state and S_(2)state are estimated at 4.608 e V and 6.889 e V,respectively.In addition,the energy values of the conical intersections of S_(1)/S and S_(2)/S_(1)are predicted to be 5.600 e V and 6.774 e V.According to the topological structures and energy values of the S_(2)/S_(1)and S_(1)/S conical intersections,the photophysical behavior of benzene excited to the S_(2)state and the effects of the S_(2)/S_(1)and S_(1)/S conical intersections are discussed in detail.
基金was supported by the National Natural Science Foundation of China(No.21733006 and No.21825303)NSFC Center for Chemical Dynamics(No.21688102)+1 种基金the Strategic Priority Research Program of Chinese Academy of Sciences(No.XDB17000000)the Chinese Academy of Sciences,and the Key Research Program of the Chinese Academy of Sciences
文摘Within the Born-Oppenheimer(BO)approximation,nuclear motions of a molecule are often envisioned to occur on an adiabatic potential energy surface(PES).However,this single PES picture should be reconsidered if a conical intersection(CI)is present,although the energy is well below the CI.The presence of the CI results in two additional terms in the nuclear Hamiltonian in the adiabatic presentation,i.e.,the diagonal BO correction(DBOC)and the geometric phase(GP),which are divergent at the CI.At the same time,there are cusps in the adiabatic PESs.Thus usually it is regarded that there is numerical difficulty in a quantum dynamics calculation for treating CI in the adiabatic representation.A popular numerical method in nuclear quantum dynamics calculations is the Sinc discrete variable representation(DVR)method.We examine the numerical accuracy of the Sinc DVR method for solving the Schrodinger equation of a two dimensional model of two electronic states with a CI in both the adiabatic and diabatic representation.The results suggest that the Sinc DVR method is capable of giving reliable results in the adiabatic representation with usual density of the grid points,without special treatment of the divergence of the DBOC and the GP.The numerical uncertainty is not worse than that after the introduction of an arbitrary vector potential for accounting the GP,whose accurate form usually is not easy to obtain.
基金JSPS Research Fellowships for Young Scientistssupported in part by JST SPRING,Japan(Nos.JPMJSP2106 and JPMJSP2180,Takuya Tanaka.and Yuki Sawatari.)+1 种基金MEXT/JSPS KAKENHI grants(No.23H02036,Gen-ichi Konishi)Murata Science and Education Foundation(Gen-ichi Konishi)。
文摘Aggregation-induced emission luminogens(AIEgens)exhibit viscosity-responsive behavior resembling those of molecular rotors;however,their response mechanisms are more complex and cannot be adequately described using simple rotational models.AIEgens demonstrate intricate dynamics that are highly dependent on their molecular structures.In this study,we synthesized water-soluble derivatives of representative AIEgens,including tetraphenylethene(TPE),bis(N,N-dialkylamino)anthracene(BDAA),and bridged stilbene,and systematically investigated the dependence of their photophysical properties in water/glycerol mixed solvents on temperature and viscosity.To elucidate the origin of their viscosity responsiveness,quantum chemical calculations were conducted to analyze their potential energy surfaces(PESs).The results revealed that compared to typical molecular rotors,these AIEgens exhibit significantly higher sensitivity to viscosity in low-viscosity regions.Notably,for TPE and BDAA derivatives,the viscosity responsiveness was found to be governed not by the activation energy barrier(ΔE_(a))based on the PES,but rather by the viscosity-dependent constraints on molecular structural changes.Furthermore,molecules possessing multiple aromatic rings or large,flexible,rotatable moieties were found to exhibit enhanced sensitivity to viscosity due to increased frictional interactions in solutions.This study provides critical insights into the mechanistic origins of the viscosity responsiveness of AIEgens,thereby advancing the fundamental understanding of their behavior and expanding their potential application as viscositysensitive probes.
基金supported by the National Natural Science Foundation of China(Nos.22103084 and 22233003 to Jiayu Huang,and No.22288201 to Dong H.Zhang)the Innovation Program for Quantum Science and Technology(No.2021ZD0303305)to Dong H.Zhangthe Dalian Innovation Support Program(No.2021RD05)to Dong H.Zhang.
文摘We constructed a new set of diabatic poten-tial energy surfaces(PESs)for the two low-est states involved in Li+Li_(2)reaction by us-ing the fundamental-invariant neural net-work method.The Li_(3)system exhibits a coni-cal intersection(CI)at the geometric D_(3)h symmetries with the energy of the CI point significantly lower than the ground-state en-ab initio ergy of the diatomic molecule.The diabaitc PESs accurately reproduce adiabatic en-ergies,derivative coupling,and energy gradient information,thereby providing a high-fideli-ty description of the CI between the two lowest electronic states.Quantum dynamical calcu-lations have revealed significant non-adiabatic effects in the Li+Li_(2)reaction.
基金supported by the National Natural Science Foundation of China(No.22288201)the Inno-vation Program for Quantum Science and Technology(No.2021ZD0303305)the Dalian Innovation Sup-port Program(No.2021RD05).
文摘A new two-state diabatic potential energy matrix(DPEM)for H3 has been constructed,based on the fun-damental invariant neural network(FI-NN)diabatization method pro-posed in our previous work[Phys.Chem.Chem.Phys.21,15040(2019)].In that initial effort,a two-state DPEM was constructed only with a 10 eV energy threshold.The current work aims to expand the en-ergy range and improve the accura-cy of DPEM.This is achieved by the utilization of full configuration inter-action(FCI)with aug-cc-pVnZ ba-sis sets and complete basis set(CBS)extrapolation.The original dataset is augmented with additional points with higher adiabatic energies,which give rise to a total of 10985 data points.The DPEM constructed in this work now enables accurate representation of adiabatic energies up to 18 eV.Quantum dynamic calculations based on this DPEM are nearly identical to those obtained from benchmark surfaces,which makes it the most accurate DPEM for the H3 system to date,therefore facilitating detailed exploration of reaction mechanisms at higher collision energies.
基金This work was supported by the National Natu- ral Science Foundation of China （No.21033002 and No.21202032） and the National Basic Research Pro- gram of China （No.2013CB834604）.
文摘The decay dynamics of N, N-dimethylthioacetamide after excitation to the S3（ππ＊） state was studied by using the resonance Raman spectroscopy and complete active space self- consistent field method calculations. The UV-absorption and vibrational spectra were as- signed. The A-band resonance Raman spectra were obtained in acetonitrile, methanol and water with the laser excitation wavelengths in resonance with the first intense absorption band to probe the Franck-Condon region structural dynamics. The CASSCF calculations were carried out to determine the excitation energies and optimized structures of the lower- lying singlet states and conical intersection point. The A-band structural dynamics and the corresponding decay mechanism were obtained by the analysis of the resonance Raman in- tensity pattern and the CASSCF calculated structural parameters. The major decay channel of S3,FC （ππ＊）→S3（ππ＊）/S1 （nπ＊）→S1（nπ＊） is proposed.
文摘Herein we have employed high-level multi-reference CASSCF and MS-CASPT2 electronic structure methods to systematically study the photochemical mechanism of intramolecularly hydrogen-bonded 2-（2＇-hydroxyphenyl）-4-methyloxazole. At the CASSCF level, we have optimized minima, conical intersections, minimum-energy reaction paths relevant to the excited-state intramolecular proton transfer （ESIPT）, rotation, photoisomerization, and the excited-state deactivation pathways. The energies of all structures and paths are refined by the MS-CASPT2 method. On the basis of the present results, we found that the ESIPT process in a conformer with the OH... N hydrogen bond is essentially barrierless process; whereas, the ESIPT process is inhibited in the other conformer with the OH... O hydrogen bond. The central single-bond rotation of the S1 enol species is energetically unfavorable due to a large barrier. In addition, the excited-state deactivation of the S1 keto species, as a result of the ultrafast ESIPT, is very efficient because of the existence of two easily-approached keto S1/S0 conical intersections. In stark contrast to the S1 keto species, the decay of the S1 enol species is almostly blocked. The present theoretical study contributes valuable knowledge to the understanding of photochemistry of similar intramolecularly hydrogen-bonded molecular and biological systems.
基金ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China （No.21033002 and No.21202032） and the National Basic Research Program of China （No.2013CB834604）.
文摘The photophysics of 3-dimethylamino-2-methyl-propenal （DMAMP） after excitation to the S2 （ππ^＊） electronic state was studied using the resonance Raman spectroscopy and complete active space self-consistent field method calculations. The transition barriers of the ground state tautomerization reactions between DMAMP and its three isomers were determined at B3LYP/6-311＋＋G（d,p） level of theory. The vibrational spectra were assigned. The A- band resonance Raman spectra were obtained in acetonitrile with excitation wavelengths in resonance with the first intense absorption band to probe the structural dynamics of DMAMP. The B3LYP-TD computation was carried out to determine the relative A-band resonance Raman intensities of the fundamental modes, and the result indicated that the vibronic-coupling existed in Franck-Condon region. Complete active space self-consistent field （CASSCF） calculations were carried out to determine the excitation energies of the lower-lying singlet and triplet excited states, the conical intersection points and the intersystem crossing points. The A-band short-time structural dynamics and the corresponding decay dynamics of DMAMP were obtained by analysis of the resonance Raman intensity pattern and CASSCF computations. It was found that a sudden de-conjugation between C1=O6 and C2=C3 occurred at the Franck-Condon region of the S2（ππ^＊） state, while the enhancement of the conjugation interaction between C3 and N（CH3）2, and between C1 and C2 evolutions shortly after the wavepacket leaves away the Pranck-Condon region via the excited state charge redistribution. The de-conjugation interaction between C1=O6 and C2=C3 made the rotation of C3=N（CH3）2 group around the C2-C3 bond much easier, while the enhanced conjugation between C1 and C2, and between C3 and N（CH3）2 made the rotation around the C1-C2 bond and C3-N5 more difficult. It was revealed that the initial structural dynamics of DMAMP was predominantly towards the CI-I（S2/S0） point, while the opportunities towards either CI-2（S2/S0） or CI-3（S2/S0） point were negligible. Two decay channels of DMAMP from S2,FC（ππ^＊） to So or Tl,min via various CIs and ISCs were proposed.
基金supported by National Natural Science Foundation of China (NSFC, Nos. 21903030, 21933011 and 21873112)。
文摘We report that the photoinduced dynamics of the phytochrome chromophore is strongly dependent on the protonation/deprotonation states of the pyrrole ring. The on-the-fly surface hopping dynamics simulations were performed to study the photoisomerization of different protonation/deprotonation phytochrome chromophore models. The simulation results indicate that the deprotonations at the pyrrole rings significantly modify the photoinduced nonadiabatic dynamics, leading to distinctive population decay dynamics and different reaction channels. Such feature can be well explained by the formation of the different hydrogen bond network patterns. Therefore, the proper understanding of the photoisomerization mechanism of phytochrome chromophore must take the hydrogen bond network into account. This work provides the new insights into the photobiological functions of phytochrome chromophore and suggests the possible ideas to control of its photoconversion processes for further rational engineering in optical applications.
基金supported by the National Natural Science Foundation of China(No.12047532,No.21733006,No.22073042,and No.22122302)。
文摘Full-dimensional adiabatic potential energy surfaces of the electronic ground state X and nine excited states A,I,B,C,D,D',D'',E' and F of H_(2)O molecule are developed at the level of internally contracted multireference configuration interaction with the Davidson correction.The potential energy surfaces are fitted by using Gaussian process regression combining permutation invariant polynomials.With a large selected active space and extra diffuse basis set to describe these Rydberg states,the calculated vertical excited energies and equilibrium geometries are in good agreement with the previous theoretical and experimental values.Compared with the well-investigated photodissociation of the first three low-lying states,both theoretical and experimental studies on higher states are still limited.In this work,we focus on all the three channels of the highly excited state,which are directly involved in the vacuum ultraviolet photodissociation of water.In particular,some conical intersections of D-E',E'-F,A-I and I-C states are clearly illustrated for the first time based on the newly developed potential energy surfaces(PESs).The nonadiabatic dissociation pathways for these excited states are discussed in detail,which may shed light on the photodissociation mechanisms for these highly excited states.
基金supported by the National Natural Science Foundation of China(No.21933011,No.21873112)。
文摘The nonadiabatic dynamics of methyl nitrate(CH_(3)ONO_(2))is studied with the on-the-fy trajectory surface hopping dynamics at the ADC(2)level.The results confirmed the existence of the ultrafast nonadiabatic decay to the electronic ground state.When the dynamics starts from S_(1) and S_(2),the photoproducts are CH_(3)O+NO_(2),consistent with previous results obtained from the experimental studies and theoretical dynamics simulations at more accurate XMS-CASPT2 level.The photolysis products are CH_(3)O+NO_(2) at the ADC(2)level when the dynamics starts from S3,while different photolysis products were obtained in previous experimental and theoretical works.These results demonstrate that the ADC(2)method may still be useful for treating the photolysis mechanism of CH_(3)ONO_(2) at the long-wavelength UV excitation,while great caution should be paid due to its inaccurate performance in the description of the photolysis dynamics at the short-wavelength UV excitation.This gives valuable information to access the accuracy when other alkyl nitrates are treated at the ADC(2)level.
文摘Herein we have employed the MS-CASPT2//CASSCF method to study the S1 excited-state intramolecular proton transfers （ESIPTs） of recently synthesized ortho-hydroxyl GFP core chromophores, i.e. OHIM, CHBDI, and MHBID, and their excited-state relaxation pathways. We have found that in OHIM and CHBDI, the ESIPT process is associated with small barriers of 3.4 and 4.2 kcal/mol; while, in MHBDI, it becomes essentially barrierless. Moreover, we have found two main S1 excited-state radiationless channels. In the first one, the enol S1 species decays to the So state via the enol S1/S0 conical intersection after overcoming considerable barriers of 7.0 and 7.7 kcal/mol in OHIM and CHBDI （however, in MHBDI, it is nearly barrierless）. In the second one, the keto S] species is first generated through the ESIPT event; then, it is de-excited into the So state in the vicinity of the keto S1/S0 conical intersection. These energetically allowed excited-state decay channels rationalize ex- perimentally observed ultralow fluorescence quantum yields. The insights gained from the present work may help to guide the design of new ortho-hydroxyl GFP core chromophores with improved fluorescence emission and brightness.
基金supported in part by MEXT/JSPS KAK-ENHI grants 23H02036(G.K.)JP23H04631,JP23K26670,JP23H03833,JP24K01471,JP24K01515(K.M.)+8 种基金JP23K01977,JP23K20039,JP25K01678(K.O.)24K08341(S.S.)Toyota Riken Scholar(K.M.)the Yoshida Aca-demic and Educational Promotion Foundation(K.M.)the Environment Research and Technology Development Fund(grant number 3RA-2502)of the Environmental Restoration and Conservation Agency provided by Ministry of the Environment of Japan(K.M.)Kyushu University Platform of Inter-/Transdisciplinary Energy Research(Q-PIT)Module-Research Program(K.M.)Kyushu University Integrated Initiative for Designing Future Society(K.M.)JST SPRING,Grant Number JPMJSP2180(T.T.)Network Joint Research Center for Materials and Devices(20253036)(K.I.)The Creative Research Encouragement Award,School of Materials and Chemical Technology,Institute of Science Tokyo(G.K.)。
文摘Aggregation-induced emission luminogens(AIEgens)are typically largeπ-conjugated molecules,but their low affinity and noninvasiveness toward analytes limit practical applications.To address this,smaller,more planar AIEgens are needed.Stilbene,though structurally suitable,lacks visible luminescence.Here,we report a minimally modified stilbene-based AIEgen-4-dipropylamino-4'-cyano-bridged stilbene(DpCBS[7])-that exhibits fluorescence solvatochromism and efficient AIE across a broad polarity range in the visible region.DpCBS[7]exhibits low quantum yields(Φ_(fl)=0.010.04)in solvents from nonpolar n-hexane to polar dimethyl sulfoxide,with large Stokes shifts,viscosity-sensitive luminescence,and highly efficient solid-state luminescence(Φ_(fl)=0.70).To elucidate its dual solvatochromic and AiE behavior,femtosecond transient absorption spectroscopy was conducted.In solution,DpCBS[7]displays transient absorption with lifetimes of 21 ps(toluene)and 56 ps(acetonitrile)at 293 K,indicating ultrafast nonradiative decay leading to low Φ_(fl).Arrhenius analysis over the temperature range of 263-313 K revealed activation energies(ΔE_(a))of 9.90kJ/mol in toluene and 12.8 kJ/mol in acetonitrile for the S_(1)→S_(0) decay of DpCBS[7].The ΔE_(a) values show no clear systematic dependence on solvent polarity.In contrast,pre-exponential factor A remains consistently high regardless of solvent polarity,indicating that the striking photophysical response is governed primarily by the pre-exponential factor rather than by modulation of the activation energy.These findings highlight the fundamental importance of tailoring the distribution function through structural modification as a robust strategy to control AiE characteristics.
基金National Natural Science Foundation of China,Grant/Award Numbers:21788102,2017YFA0204501。
文摘We computationally investigated the molecular aggregation effects on the excited state deactivation processes by considering both the direct vibrational relaxation and the S0/S1 surface crossing,that is,the minimum energy conical intersection(MECI).Taking classical AIEgens bis(piperidyl)anthracenes(BPAs)isomers and the substituted silole derivatives as examples,we show that the deformation ofMECI always occurs at the atom with greater hole/electron overlap.Besides,the energetic and structural changes of MECI caused by substituent has been investigated.We find that effective substituent such as the addition of the electron-donating groups,which can polarize the distribution of hole/electron density of molecules,will lead to the pyramidalization deformation of MECI occurring at the substituent position and simultaneously reduce the required energy to reach MECI.And MECI is sterically restricted by the surrounding molecules in solid phase,which remarkably hinders the non-radiative decay through surface crossing.Through quantitative computational assessments of the fluorescence quantum efficiency for both solution and solid phases,we elucidate the role of MECI and its dependence on the substitutions through pyramidalization deformation,which give rise to the aggregation-induced emission(AIE)phenomenon for 9,10-BPA,to aggregation-enhance emission(AEE)behavior for 1,4-BPA,and to conventional aggregation-caused quenching(ACQ)for 1,5-BPA.We further verify such mechanism for siloles,for which we found that the substitutions do not change the AIE behavior.Our findings render a general molecular design approach to manipulating the aggregation effect for optical emission.
文摘When femtosecond （fs） timeresolved experiments are used to study ultrafast processes, quantum beat phenomena are often observed. In this paper, to analyze the fs timeresolved spectra, we will present the density matrix method, a powerful theoretical technique, which describes the dynamics of population and coherence of the system. How to employ it to study the pumpprobe experiments and fs ultrafast processes is described. The transition of pyrazine is used as an example to demonstrate the application of the density matrix method. Recently, Suzuki＇s group have employed the 22 fs time resolution laser to study the dynamics of the state of pyrazine. In this case, conical intersection is commonly believed to play an important role in this nonadiabatic process. How to treat the effect of conical intersection on nonadiabatic processes and fs timeresolved spectra is presented. Another important ultrafast process, vibrational relaxation, which takes place in subps and ps range and has never been carefully studied, is treated in this paper. The vibrational relaxation in water dimer is chosen to demonstrate the calculation. It should be noted that the vibrational relaxation of （H20）2 has not been experimentally studied but it can be accomplished by the pump-probe experiments.
