Non-adiabatic dynamics simulation exploration of the wavelength-dependent photoinduced relaxation mechanism of trans-N-1-methyl-2-(tolylazo) imidazole in the gas phase

Li, Zhao; Zhou, Panwang; Zhao, Guangjiu

doi:10.1039/c6ra11416d

Cited by 16 publications

(18 citation statements)

References 41 publications

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“…In addition, t 0 and τ represent, respectively, the starting time for decay and the decay time constant. It should be noted that the initial 76 fs is excluded for the nonobvious decay of the S 1 state during this period as used in several previous publications. , The fitting results suggest two decay times of 109 and 670 fs, which are of the same order but shorter than the experimentally measured values of 440 and 1.4 fs. The longer experimental values could be caused by the steric-hindrance effect of the solvent molecules.…”

Section: Results and Discussionmentioning

confidence: 73%

Position of the Benzene Ring Substituent Regulates the Excited-State Deactivation Process of the Benzyluracil Systems

Zheng

Zhan

et al. 2020

J. Phys. Chem. A

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A systematic theoretical study of the regulating effect of the substituent position on the photoinduced deactivation process of the benzyluracil systems has been performed based on the high-level static electronic structure calculations and on-the-fly full-dimensional excited-state dynamics simulations. Similarities and differences coexist for the two systems by comparative studies on the photoinduced deactivation process of the 5-benzyluracil (5-BU) and 6-benzyluracil (6-BU) systems. They both obey an S2 → S1 → S0 two-step decay pattern, and the decay coordinates of the S2 → S1 and S1 → S0 processes are mainly driven by the elongation of the bridging bond and the out-of-plane ring deformation motion, respectively. However, the puckering motion occurring at the C2 atom in the uracil fragment dominates the decay pathway of the 5-BU system. On the contrary, the puckering motion at the C5 atom in the benzene fragment mainly drives the decay coordinate of the 6-BU system. Therefore, the substituent position could play significant roles in the deactivation process of the benzyluracil systems. Moreover, the S1 → S0 decay process of the 6-BU system consists of five pathways, possessing a more complex deactivation picture than the 5-BU system. The fitted time scale of the puckering motion is compatible with the experimentally observed lifetimes. This work provides a fundamental understanding of the photophysical and photochemical properties of the benzyluracil systems and can give rational suggestions to further design or regulate the bionic molecular systems.

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Section: Results and Discussionmentioning

confidence: 73%

Position of the Benzene Ring Substituent Regulates the Excited-State Deactivation Process of the Benzyluracil Systems

Zheng

Zhan

et al. 2020

J. Phys. Chem. A

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“…We have simulated the trans - cis photoreaction of SAOMe by nonadiabatic surface-hopping dynamics with the NAIMD-DICP package. − In this package, nuclear motion is represented by the classical trajectory obtained using Newton’s equations. The integration of the classical equations is performed by means of the velocity-Verlet algorithm .…”

Section: Methodsmentioning

confidence: 99%

“…The reliability of this theoretical level has been proven previously in the investigation of the nonadiabatic dynamic simulations of similar molecules. 28,30,31 Moreover, CASPT2 calculations were performed to confirm the reaction pathway obtained by the dynamics simulations.…”

Section: Methodsmentioning

confidence: 99%

Ultrafast Photoisomerization of N-(2-Methoxybenzylidene)aniline: Nonadiabatic Surface-Hopping Study

Gao

Wang

2021

J. Phys. Chem. A

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We investigated the ultrafast photoisomerization of N-(2-methoxybenzylidene)aniline in the gas phase excited into the second singlet (S 2 ) state by nonadiabatic surface-hopping dynamics calculations. Two trans isomers (1E and 1E') were taken into consideration in our dynamics simulation. Three conical intersections (CIs) were characterized in the optimization. The CI between S 2 and the first singlet (S 1 ) states presents a nearly planar structure, while the other two CIs (CI twist -I and CI twist -II) between S 1 and the ground (S 0 ) states show nearly perpendicular geometries. After two trans isomers excited to the S 2 state, the torsion of the C−N bond connected the phenyl group and the stretch of the central bridging bond make the molecule reach CI planar , and the S 2 /S 1 hopping occurs. During the S 1 -state dynamics, the molecule moves to a S 1 /S 0 CI (CI twist -I or CI twist -II) by the rotation of the central bridging bond. The cis isomer is obtained through a barrierless pathway in the S 0 state with the torsion of the three bridging bonds. There is a main channel and an alternative one for the photoisomerization process of both trans isomers. CI twist -I and CI twist -II act as S 1 /S 0 decay funnels in the main isomerization channels of 1E and 1E' isomers, respectively, and the photochemical processes of 1E and 1E' lead to different cis isomers.

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“…The ultrafast photoinduced dynamics were studied by nonadiabatic ab initio surface‐hopping simulations using the NAIMD‐DICP package. This package has been successfully used to investigate the photoisomerization of several systems such as azobenzene, bridged azobenzene, and isolated green fluorescent protein chromophore anion . Surface hopping, mean‐field, the method combining them, and multiple spawning are the most widely used approaches to account for nonadiabatic effects.…”

Section: Computational Detailsmentioning

confidence: 99%

The keto→enol photoisomerization of N‐salicilydenemethylfurylamine: Nonadiabatic ab initio dynamics simulation

Gao

Wang

2018

Int J of Quantum Chemistry

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The photoinduced isomerization of cis-keto and trans-keto isomers in N-salicilydenemethylfurylamine has been studied using the surface-hopping approach at the CASSCF level of theory. After the cis-keto or trans-keto isomer is excited to S 1 state, the molecule initially moves to a excitedstate local minimum. The torsional motion around relative bonds in the chain drives the molecule to approach a keto-form conical intersection and then nonadiabatic transition occurs. According to our full-dimensional dynamics simulations, the trans-keto and enol photoproducts are responsible for the photochromic effect of cis-keto isomer excited to S 1 state, while no enol isomer was obtained in the photoisomerization of trans keto on excitation. The cis keto to enol and cis keto to trans keto isomerizations are reversible photochemical reactions. It is confirmed that this aromatic Schiff base is a potential molecular switch. Furthermore, the torsion of CAN bond occurs in the radiationless decay of trans-keto isomer, while it is completely suppressed by an intramolecular hydrogen bonding interaction in the dynamics of cis-keto form. Moreover, the excited-state lifetime of cis keto is longer than that of trans-keto form due to the OÁÁÁHAN hydrogen bond.aromatic Schiff base, conical intersection, dynamics simulations, keto-enol photoisomerization, Zhu-Nakamura theory 1 | I N TR ODU C TI ON Photochromism is a phenomenon that occurs in the ultrafast photochemical reactions in nature, including processes such as photochemical ringclosure or ring-opening reactions, cis-trans or trans-cis isomerization, or intramolecular proton transfer. [1] The photochromism phenomena have attracted great attention for technological application as optical data processing, high-density information storage devices, logic devices, photoswitches, and light-driven molecular motors. [2][3][4][5][6][7][8][9] It is noteworthy that the photochromic and thermochromic properties of aromatic Schiff bases have been widely investigated both experimentally and theoretically. [10][11][12][13][14][15][16][17][18][19][20] It has been reported that the photochromism and thermochromism phenomena in these compounds occur due to two ultrafast processes: cis-trans or trans-cis isomerization and intramolecular proton transfer from the hydroxyl to the amino group. The ground-or excited-state intramolecular proton transfer (GSIPT or ESIPT) phenomena are of particular interest and have been studied extensively by diverse investigations. [21][22][23] During the photochemical processes of aromatic Schiff bases, the GSIPT or ESIPT behavior can result in photochromism between enol and keto tautomers. [14][15][16]19,20] N-salicilydenemethylfurylamine (SMFA) is a new salicylaldehyde Schiff base, as depicted in Figure 1. Recently, a theoretical exploration of the excited-state deactivation mechanisms of SMFA has been done with the CC2 method by Moghadam et al. [24] Excited-state reaction coordinates and potential energy profiles of the ground (S 0 ) and lowest excited singlet (S 1 ) st...

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Non-adiabatic dynamics simulation exploration of the wavelength-dependent photoinduced relaxation mechanism of trans-N-1-methyl-2-(tolylazo) imidazole in the gas phase

Abstract: A comprehensive picture of the photoinduced non-adiabatic relaxation dynamics of trans-N-1-methyl-2-(tolylazo) imidazole (trans-MTAI) in different electronic excited states has been revealed using the on-the-fly surface hopping method at the ab initio CASSCF level.

Cited by 16 publications

References 41 publications

Position of the Benzene Ring Substituent Regulates the Excited-State Deactivation Process of the Benzyluracil Systems

Position of the Benzene Ring Substituent Regulates the Excited-State Deactivation Process of the Benzyluracil Systems

Ultrafast Photoisomerization of N-(2-Methoxybenzylidene)aniline: Nonadiabatic Surface-Hopping Study

The keto→enol photoisomerization of N‐salicilydenemethylfurylamine: Nonadiabatic ab initio dynamics simulation

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