Nonadiabatic dynamics simulation of photoisomerization mechanism of the second stablest isomer of N-salicilydenemethylfurylamine

Gao, Aihua; Li, Jianpeng; Wang, Meishan; Ma, Xiao‐Guang

doi:10.1016/j.saa.2017.10.041

Cited by 7 publications

(13 citation statements)

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“…The atom number scheme of SMFA used in this work is presented in Figure . It was found that CI(1–8) play important roles after the photoexcitation of the enol isomer . The main subject of this work is analyzing the photoisomerization pathways of the cis ‐keto and trans ‐keto isomers ( S 0‐ cis ‐keto and S 0‐ trans ‐keto, see Figure and Supporting Information Figure S2).…”

Section: Resultsmentioning

confidence: 99%

“…In this work, 41 trajectories and 27 trajectories were calculated with a 0.5 fs time step for isomerization processes of cis ‐keto and trans ‐keto isomers in SMFA, respectively; around the minimum energy CIs, the time step was set to 0.1 fs. The required energies and gradients were evaluated on the fly at each time step at the two‐state‐averaged CASSCF(6,6)/6–31G level, which was used in the photoisomerization investigation of the enol isomers in SMFA . The active spaces used in the CASSCF(6,6)/6–31G calculation were presented in Figure .…”

Section: Computational Detailsmentioning

confidence: 99%

“…According to ab initio dynamics simulations, the trans ‐keto and cis ‐keto isomers were obtained as photoproducts. In our previous work, it was found that the two stablest isomers of SMFA ( cis enol‐1 and cis enol‐2 in Figure ) are both in enol form and they have similar UV spectra . Thus, static electronic structure calculations and surface‐hopping dynamics simulations were carried out to explore the photoisomerization processes of the second stablest isomer of SMFA.…”

Section: Introductionmentioning

confidence: 99%

“…Previous static quantum chemical calculations and dynamics simulations have provided the detailed mechanisms of photoinduced enol→keto processes in SMFA. For aromatic Schiff bases, such as SMFA, salicylideneaniline, salicylidene methylamine, fewer studies were done to investigate the photochemical behavior in keto→enol isomerization. According to our previous studies, the simulations of enol isomer in SMFA generate three species in the S 0 state: the enol, cis ‐keto, and trans ‐keto forms .…”

Section: Introductionmentioning

confidence: 99%

“…For aromatic Schiff bases, such as SMFA, salicylideneaniline, salicylidene methylamine, fewer studies were done to investigate the photochemical behavior in keto→enol isomerization. According to our previous studies, the simulations of enol isomer in SMFA generate three species in the S 0 state: the enol, cis ‐keto, and trans ‐keto forms . In this work, full‐dimensional nonadiabatic ab initio dynamics simulations were performed to understand the photoinduced processes of cis ‐keto and trans ‐keto isomers in SMFA at the complete active space self‐consistent field (CASSCF) level.…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Resultsmentioning

confidence: 99%

Section: Computational Detailsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%