Photochemistry of DNA Fragments via Semiclassical Nonadiabatic Dynamics

被引:48
作者
Alexandrova, Anastassia N. [1 ]
Tully, John C. [1 ]
Granucci, Giovanni [2 ]
机构
[1] Yale Univ, Dept Chem, New Haven, CT 06520 USA
[2] Univ Pisa, Dipartimento Chim & Chim Ind, I-56126 Pisa, Italy
关键词
EXCITED-STATE DYNAMICS; ULTRAFAST INTERNAL-CONVERSION; ELECTRONIC RELAXATION DYNAMICS; RADIATIONLESS DECAY MECHANISM; INITIO MOLECULAR-DYNAMICS; AB-INITIO; FLUORESCENCE PROPERTIES; CONICAL INTERSECTIONS; NONRADIATIVE DECAY; ADENINE-THYMINE;
D O I
10.1021/jp103322c
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Forming upon absorption of a UV photon, excited states of DNA are subject to nonadiabatic evolution, via either internal conversion (IC) back to the ground state or mutagenesis. Nonadiabatic processes following the formation of the first singlet excited states, S1, in 10 different small DNA fragments-4 single 4'H-nucleosides, 2 Watson-Crick base pairs, and 4 nucleotide quartets have been investigated. Simulations were done via the nonadiabatic direct trajectory surface hopping semiclassical dynamics. The electronic wave function was obtained with configuration interaction, based on the semiempirical AM1 and PM3 Hamiltonians with fractional orbital occupation numbers. The evolution of the electronic wave function was governed by the time-dependent Schrodinger equation with a locally diabatic representation, intrinsically stable near surface crossings. The nuclei evolved on adiabatic potential energy surfaces, as prescribed by classical Newtonian dynamics, with sudden hops between potential energy surfaces to account for nonadiabatic transitions. The "fewest switches" surface hopping algorithm coupled the quantum and classical parts of the system. The dynamics simulations revealed several routes of nonadiabatic relaxation in these systems, which were not reported previously, and also recovered known routes of IC.
引用
收藏
页码:12116 / 12128
页数:13
相关论文
共 84 条
[1]   Photophysics of the π,π* and n,π* States of Thymine: MS-CASPT2 Minimum-Energy Paths and CASSCF on-the-Fly Dynamics [J].
Asturiol, David ;
Lasorne, Benjamin ;
Robb, Michael A. ;
Blancafort, Lluis .
JOURNAL OF PHYSICAL CHEMISTRY A, 2009, 113 (38) :10211-10218
[2]   ELECTRONIC-SPECTRA AND TRANS CIS PHOTOISOMERISM OF CARBOCYANINES - A THEORETICAL (CS INDO CI) AND EXPERIMENTAL-STUDY [J].
BARALDI, I ;
CARNEVALI, A ;
MOMICCHIOLI, F ;
PONTERINI, G .
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY, 1993, 49 (04) :471-495
[3]   Nonadiabatic deactivation of 9H-adenine:: A comprehensive picture based on mixed quantum-classical dynamics [J].
Barbatti, Mario ;
Lischka, Hans .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (21) :6831-6839
[4]   Excited-state potential energy surface for the photophysics of adenine [J].
Blancafort, L .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (01) :210-219
[5]   Key role of a threefold state crossing in the ultrafast decay of electronically excited cytosine [J].
Blancafort, L ;
Robb, MA .
JOURNAL OF PHYSICAL CHEMISTRY A, 2004, 108 (47) :10609-10614
[6]   Energetics of cytosine singlet excited-state decay paths - A difficult case for CASSCF and CASPT2 [J].
Blancafort, Lluis .
PHOTOCHEMISTRY AND PHOTOBIOLOGY, 2007, 83 (03) :603-610
[7]   Ultrafast deactivation channel for thymine dimerization [J].
Boggio-Pasqua, Martial ;
Groenhof, Gerrit ;
Schaefer, Lars V. ;
Grubmueller, Helmut ;
Robb, Michael A. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (36) :10996-+
[8]   Excited states dynamics of DNA and RNA bases: Characterization of a stepwise deactivation pathway in the gas phase [J].
Canuel, C ;
Mons, M ;
Piuzzi, F ;
Tardivel, B ;
Dimicoli, I ;
Elhanine, M .
JOURNAL OF CHEMICAL PHYSICS, 2005, 122 (07)
[9]   Ab initio study on deactivation pathways of excited 9H-guanine [J].
Chen, H ;
Li, SH .
JOURNAL OF CHEMICAL PHYSICS, 2006, 124 (15)
[10]   Theoretical study toward understanding ultrafast internal conversion of excited 9H-adenine [J].
Chen, H ;
Li, SH .
JOURNAL OF PHYSICAL CHEMISTRY A, 2005, 109 (38) :8443-8446