【摘 要】
：
An efficient implementation of local excitation approximation(LEA)approach is presented for predicting the blueshift of the local n→π* electronic vertical excitation in condensed phase at ab initio le
【机 构】
：
School of Chemistry and Chemical Engineering,Key Laboratory of Mesoscopic Chemistry of Ministry of E
论文部分内容阅读
An efficient implementation of local excitation approximation(LEA)approach is presented for predicting the blueshift of the local n→π* electronic vertical excitation in condensed phase at ab initio level.We propose a new localizing procedure to obtain regional local molecular orbitals(RLMO)using singular value decomposition(SVD)algorithm.[1] The main idea of the LEA scheme is that the only local electron excitations within selected reference subspace are treated to calculate the target excited state wavefunctions.This concept is realized by using the localized molecular orbitals(LMO)localized on the chromophore substructure.For the target transitions which show the strong local character within the chromophore region,the LEA scheme can provide excited state properties without much loss of accuracy.Using this LEA scheme and molecular dynamics simulation,we study the solvent effect on the local n→π* excitation energy in formaldehyde and acetone in aqueous solution.Statistical analyses using 600 configurations generated from molecular dynamics simulation are presented for acetone and formaldehyde,respectively.The blueshift in the n→π* vertical electronic excitation energy was 1453±52 cm-1 for acetone and 1490±53 cm-1 for formaldehyde.The results are in good agreement with the available experimental blue shift of 1500±200 cm-1.
其他文献
The intrinsic reaction coordinate computations and ab initio molecular dynamic simulations at CASPT2//CASSCF/cc-PVDZ level of theory were used to deeply understand the photo-dissociation dynamics of O
In this work a CASPT2//CASSCF/AMBER QM/MM approach was employed to investigate the isomerization and protonation reactions upon photoexcitation of the wild-type PYP.The study provides a comprehensive
Density functional calculations were performed to investigate the interaction of histidine,phenylalanine,tryptophan and tyrosine with the outer surface of different charged(7,7)single-walled carbon na
In this work,we selected a series of halogen-bond complexes formed between F-X(X=F,Cl,Br,I)and ammonia as models; in addition,a hydrogen-bond complex formed between F-H and ammonia was also selected f
本文采用运动方程耦合簇(EOM-CC)方法[1-2]考察了AuH2 的基态和能量较低的一些电子态(2∑+α 态,2∑+g 态,2△g 态和2Πg态)的性质。结合我们课题组所发展的处理闭壳层体系自旋轨道耦合(SOC)的耦合簇方法[3-5],考察了SOC 效应对这些态的能量、平衡构型和振动频率的影响。通过包含更高激发贡献的EOMIP-CCSDT-3 方法我们还考察了三重激发对该体系性质的影响。我们的结
To find which vibration mode probably becomes an access for electron transfer from donor(C343)to acceptor(TiO2),when there is ultra electron transfer occurring,and the configuration of donor can not h
An important application of the density matrix method to chemistry is the description of the relaxation of both vibrational and electronic excited states.[1] For this purpose the so-called Bixon-Jortn
A combined approach of the multiconfigurational perturbation theory with Rice-Ramsperger-Kassel-Marcus methodology has been employed to calculate the minimum potential energy profiles and the rates of
It is a long-standing controversy whether the whole metal clusters are saturated with dissolved carbon atoms during the growth of single-walled carbon nanotubes(SWCNTs).In current work,we are trying t
芘醇作为芘的羟基取代物其酸性随着电子态的激发而增强而被称之为“光酸”.光酸分子激发态的酸性增强来源于分子偶极矩随分子电子态激发态的变化,并且偶极矩影响着分子的光谱性质,通过理论计算芘醇的电子吸收谱及共振拉曼谱可以很好地给出芘醇分子随着光激发的偶极矩变化信息.芘醇的最低的两个ππ*电子激发态分别被称作1La 态与1Lb 态,在激发态质子转移的过程中这两个电子态的能级会发生反转：质子化态第一激发态对应