Iterative diagonalization in the state-averaged multi-configurational time-dependent Hartree approach: excited state tunneling splittings in malonaldehyde

An iterative block Lanczos-type diagonalization scheme utilizing the state-averaged multi-configurational time-dependent Hartree (MCTDH) approach is introduced. Combining propagation in real and imaginary time and using a set of initial seed wavefunctions corresponding to excitations via the different components of the dipole moment vector, the scheme can favorably be used to selectively compute vibrational states which show high intensities in vibrational absorption spectra. Tunneling splitted vibrational states in double well systems can be described particularly efficient employing an increased set of seed wavefunctions which includes symmetric and anti-symmetric wavefunctions simultaneously. The new approach is used to study the tunneling splittings of the vibrationally excited states of malonaldehyde. Full-dimensional multi-layer MCTDH calculations are performed and results for the tunneling splittings of several excited vibrational states can be obtained. The calculated tunneling splittings agree reasonably well with available experimental data. Order of magnitude differences between tunneling splittings of different vibrationally excited states are found and interpreted.     

Role of doubly excited states in calculations of optical activity

It is shown that doubly excited states play an important role in calculations of the optical activity of molecules with well-conjugated electron systems, such as the DNA bases. In some significant cases it is necessary to include a large number of excited states in the configuration interaction (CI ) to obtain a reliable, converging result. A new version of the CNDO/OPTIC method, which includes doubly excited states in the CI , is proposed. As an application, the electric transition moments in different pyrimidines are considered. The calculated results agree with experimental data and results obtained from ab initio calculations and INDO calculations using doubly excited states in the CI .     

Optimized effective potential method for individual low-lying excited states

This paper presents an optimized effective potential (OEP) approach based on density functional theory (DFT) for individual excited states that implements a simple method of taking the necessary orthogonality constraints into account. The amended Kohn-Sham (KS) equations for orbitals of excited states having the same symmetry as the ground one are proposed. Using a variational principle with some orthogonality constraints, the OEP equations determining a local exchange potential for excited states are derived. Specifically, local potentials are derived whose KS determinants minimize the total energies and are simultaneously orthogonal to the determinants for states of lower energies. The parametrized form of an effective DFT potential expressed as a direct mapping of the external potential is used to simplify the OEP integral equations. A performance of the presented method is examined by exchange-only calculations of excited state energies for simple atoms and molecules.     

A simplified relativistic time-dependent density-functional theory formalism for the calculations of excitation energies including spin-orbit coupling effect

In the present work we have proposed an approximate time-dependent density-functional theory (TDDFT) formalism to deal with the influence of spin-orbit coupling effect on the excitation energies for closed-shell systems. In this formalism scalar relativistic TDDFT calculations are first performed to determine the lowest single-group excited states and the spin-orbit coupling operator is applied to these single-group excited states to obtain the excitation energies with spin-orbit coupling effects included. The computational effort of the present method is much smaller than that of the two-component TDDFT formalism and this method can be applied to medium-size systems containing heavy elements. The compositions of the double-group excited states in terms of single-group singlet and triplet excited states are obtained automatically from the calculations. The calculated excitation energies based on the present formalism show that this formalism affords reasonable excitation energies for transitions not involving 5p and 6p orbitals. For transitions involving 5p orbitals, one can still obtain acceptable results for excitations with a small truncation error, while the formalism will fail for transitions involving 6p orbitals, especially 6p1/2 spinors.     

CASSCF/CAS-PT2 study of hole transfer in stacked DNA nucleobases

CASSCF and CAS-PT2 calculations are performed for the ground and excited states of radical cations consisting of two and three nucleobases. The generalized Mulliken-Hush approach is employed for estimating electronic couplings for hole transfer in the pi-stacks. We compare the CASSCF results with data obtained within Koopmans' approximation. The calculations show that an excess charge in the ground and excited states in the systems is quite localized on a single base both at the CASSCF level and in Koopmans' picture. However, the CASSCF calculations point to a larger degree of localization and, in line with this, smaller transition dipole moments. The agreement between the CAS-PT2 corrected energy gaps and the values estimated with Koopmans' theorem is better, with the CAS-PT2 calculations giving somewhat smaller gaps. Overall, both factors result in smaller CASSCF/CAS-PT2 couplings, which are reduced by up to 40% of the couplings calculated using Koopmans' approximation. The tabulated data can be used as benchmark values for the electronic couplings of stacked nucleobases. For the base trimers, comparison of the results obtained within two- and three-state models show that the multistate treatment should be applied to derive reliable estimates. Finally, the superexchange approach to estimate the donor acceptor electronic coupling in the stacks GAG and GTG is considered.     

Excited states in the multireference state-specific coupled-cluster theory with the complete active space reference

The recently proposed multireference state-specific coupled-cluster theory with the complete active space reference has been used to study electronically excited states with different spatial and spin symmetries. The algorithm for the method has been obtained using the computerized approach for automatic generation of coupled-cluster diagrams with an arbitrary level of the electronic excitation from a formal reference determinant. The formal reference is also used to generate the genuine reference state in the form of a linear combination of determinants contracted to a configuration with the spin and spatial symmetries of the target state. The natural-orbital expansions of the one-electron configuration inferaction density matrix allowed us to obtain the most compact orbital space for the expansion of the reference function. We applied our approach in the calculations of singlet and triplet states of different spatial symmetries of the water molecule. The comparisons of the results with values obtained using other many-particle methods and with the full configuration interaction results demonstrate good ability of the approach to deal with electronic excited states.     

Density functional theory study of 1,2‐dioxetanone decomposition in condensed phase

The decomposition of 1,2‐dioxetanone into a CO₂ molecule and into an excited state formaldehyde molecule was studied in condensed phase, using a density functional theory approach. Singlet and triplet ground and excited states were all included in the calculations. The calculations revealed a novel mechanism for the chemiluminescence of this compound. The triplet excitation can be explained by two intersystem crossings (ISCs) with the ground state, while the singlet excitation can be accounted by an ISC with the triplet state. The experimentally verified small excitation yield can then be explained by the presence of an energy barrier present in the potential energy surface of the triplet excited state, which will govern both triplet and singlet excitation. It was also found that the triplet ground state interacts with both the triplet excited and singlet ground states. A MPWB1K/mPWKCIS approach provided results in agreement with the existent literature. © 2012 Wiley Periodicals, Inc.     

Variable metric optimization of molecular geometry in electronically excited states

The variable metric (VM) method is used to optimize molecular geometry in electronically excited states. A general expression for the first derivative of energy in the particular excited state is derived, considering configuration interaction of all singly excited configurations. A special expression for the excited states energy derivative is given for calculations with semiempirical methods of CNDO type. The geometry optimizations of a set of molecules in various excited states have been carried out by the CNDO/2 method. The results of computations have been discussed and compared with the available experimental data. A good agreement of the calculated geometries with the experimental ones has been shown in the first excited states and a relatively good agreement in the higher states, with some exceptions. Some special features of the proposed method are discussed.     

Theoretical study of the electronic spectra of square-planar platinum (II) complexes based on the two-component relativistic time-dependent density-functional theory

In the present work the electronic spectra of [PtCl(4)](2-), [PtBr(4)](2-), and [Pt(CN)(4)](2-) are studied with a recently proposed relativistic time-dependent density-functional theory (TDDFT) based on the two-component zeroth-order regular approximation and a noncollinear exchange-correlation (XC) functional. The contribution to the double group excited states in terms of singlet and triplet single group excited states is estimated through the inner product of the transition density matrix obtained from two-component and scalar relativistic TDDFT calculations to better understand the double group excited states. Spin-orbital coupling effects are found to be very important in order to simulate the electronic spectra of these complexes. The results show that the two-component TDDFT formalism can afford excitation energies with high accuracy for the transition-metal systems studied here when use is made of a proper XC potential.     

量子Monte Carlo处理激发态

提出了用于电子激发态的剩余函数变分量子ＭｏｎｔｅＣａｒｌｏ（ＳＦＶＭＣ）方法,已经证明：若激发态的初始波函数与基态的初始波函数属于对称性不同的不可约表示时,该激发态的ＳＦＶＭＣ方法与基态的ＳＦＶＭＣ方法完全相同;若激发态的初始波函数与基态的初始波函数有相同的对称性时,只要对激发态的初始波函数作正交性修正,则其态的ＳＦＶＭＣ方法亦可推到该激发态的情况。文章导出了这第二类激发态的ＳＦＶＭＣ方法的详细计     

Nonadiabatic Absorption Spectra and Ultrafast Dynamics of DNA and RNA Photoexcited Nucleobases

We have recently proposed a protocol for Quantum Dynamics (QD) calculations, which is based on a parameterisation of Linear Vibronic Coupling (LVC) Hamiltonians with Time Dependent (TD) Density Functional Theory (TD-DFT), and exploits the latest developments in multiconfigurational TD-Hartree methods for an effective wave packet propagation. In this contribution we explore the potentialities of this approach to compute nonadiabatic vibronic spectra and ultrafast dynamics, by applying it to the five nucleobases present in DNA and RNA. For all of them we computed the absorption spectra and the dynamics of ultrafast internal conversion (100 fs timescale), fully coupling the first 2–3 bright states and all the close by dark states, for a total of 6–9 states, and including all the normal coordinates. We adopted two different functionals, CAM-B3LYP and PBE0, and tested the effect of the basis set. Computed spectra are in good agreement with the available experimental data, remarkably improving over pure electronic computations, but also with respect to vibronic spectra obtained neglecting inter-state couplings. Our QD simulations indicate an effective population transfer from the lowest energy bright excited states to the close-lying dark excited states for uracil, thymine and adenine. Dynamics from higher-energy states show an ultrafast depopulation toward the more stable ones. The proposed protocol is sufficiently general and automatic to promise to become useful for widespread applications.     

Hydrogen bonding in electronically excited states of molecules

Theoretical Chemistry Accounts - CNDO/2 calculations show that hydrogen bonds in the electronically excited states of +H2O and +HOCH3 systems are slightly weaker than in the ground states. The...     

HSO自由基电子基态激发态的CAS计算研究

使用CASSCF方法和ANO-L基组优化了HSO自由基的基态和3个低占据激发态的结构, 并采用包括更多电子动态相关能的CASPT2方法进行了单点能校正. 频率计算结果表明, 优化的4个几何为势能面上的稳定点. 通过电子结构的研究合理地解释了各个激发态相对于电子基态的结构变化.     

Global topological approach to highly excited vibration: a case study of H2O, CH2Br2 and CD2Br2

A global topological approach based on the algebraic coset representation to study highly excited molecular vibration is proposed. The algorithm allows us to elucidate ample highly excited vibrational dynamics from a global viewpoint. Topics for highly excited states studied include (1) global topological structures, (2) global symmetric and antisymmetric characters, (3) resonance overlaps and chaotic motion, (4) action transfer coefficients and (5) survival probabilities denoting the decaying of the action stored in a mode, with sample calculations for H₂O, CH₂Br₂ and CD₂Br₂.     

Evaluating First-Order Molecular Properties of Delocalized Ionic or Excited States in Molecular Aggregates by Renormalized Excitonic Method

In the past few years, the renormalized excitonic model (REM) approach was developed as an efficient low-scaling ab initio excited state method, which assumes the low-lying excited states of the whole system are a linear combination of various single monomer excitations and utilizes the effective Hamiltonian theory to derive their couplings. In this work, we further extend the REM calculations for the evaluations of first-order molecular properties (e.g. charge population and transition dipole moment) of delocalized ionic or excited states in molecular aggregates, through generalizing the effective Hamiltonian theory to effective operator representation. Results from the test calculations for four different kinds of one dimensional (1D) molecular aggregates (ammonia, formaldehyde, ethylene and pyrrole) indicate that our new scheme can efficiently describe not only the energies but also wavefunction properties of the low-lying delocalized electronic states in large systems.     

Electronic states and radiative transitions in LiAr

Ab initio MRD-CI calculations have been carried out on the ground and the eight lowest excited electronic states of LiAr, correlating with excited Li atom states up to 3d ²D. The ground (X²∑⁺ (2s)) and 2 ²Σ⁺ (2p) electronic states are repulsive while the higher excited states show shallow Rydberg minima. Rates of radiative bound-bound and bound-free transitions have been also calculated.     

Excited state properties of 7-hydroxy-4-methylcoumarin in the gas phase and in solution. A theoretical study

TDDFT/B3LYP and RI-CC2 calculations with different basis sets have been performed for vertical and adiabatic excitations and emission properties of the lowest singlet states for the neutral (enol and keto), protonated and deprotonated forms of 7-hydroxy-4-methylcoumarin (7H4MC) in the gas phase and in solution. The effect of 7H4MC-solvent (water) interactions on the lowest excited and fluorescence states were computed using the Polarizable Continuum Method (PCM), 7H4MC-water clusters and a combination of both approaches. The calculations revealed that in aqueous solution the pi pi* energy is the lowest one for excitation and fluorescence transitions of all forms of 7H4MC studied. The calculated excitation and fluorescence energies in aqueous solution are in good agreement with experiment. It was found that, depending on the polarity of the medium, the solvent shifts vary, leading to a change in the character of the lowest excitation and fluorescence transition. The dipole-moment and electron-density changes of the excited states relative to the ground state correlate with the solvation effect on the singlet excited states and on transition energies, respectively. The calculations show that, in contrast to the ground state, the keto form has a lower energy in the pi pi* state as compared to enol, demonstrating from this point of view the energetic possibility of proton transfer from the enol to the keto form in the excited state.