A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP)

The recently implemented second‐order perturbation theory based on a complete active space self‐consistent field reference function has been extended by allowing the Fock‐type one‐electron operator, which defines the zeroth‐order Hamiltonian to have nonzero elements also in nondiagonal matrix blocks. The computer implementation is now less straightforward and more computer time will be needed in obtaining the second‐order energy. The method is illustrated in a series of calculations on N2, NO, O2, CH3, CH2, and F−.

Second-order perturbation theory with a complete active space self-consistent field reference function.

6. Rehybridization of the Acceptor (RICT) 3908 7. Planarization of the Molecule (PICT) 3909 III. Fluorescence Spectroscopy 3909 A. Solvent Effects and the Model Compounds 3909 1. Solvent Effects on the Spectra 3909 2. Steric Effects and Model Compounds 3911 3. Bandwidths 3913 4. Isoemissive Points 3914 B. Dipole Moments 3915 C. Radiative Rates and Transition Moments 3916 1. Quantum Yields and Radiationless Deactivation Processes 3916

Structural Changes Accompanying Intramolecular Electron Transfer: Focus on Twisted Intramolecular Charge-Transfer States and Structures

Molcas: a program package for computational chemistry.

The second-order approximate coupled cluster singles and doubles model CC2

Second-order perturbation theory based on a CASSCF reference state is derived and implemented. The first-order wave function includes the full space of interacting states. Expressions for the contributions to the second-order energy are obtained in terms of up to four-particle density matrices for the CASSCF reference state. The zeroth-order Hamiltonian reduces to the MOller-Plesset Hamiltonian for a closed-shell reference state. The limit of the implementation is given by the number of active orbitals, which determines the size of the density matrices. It is presently around 13 orbitals. The method is illustrated in a series of calculations on H 2 , H 2 O, CH 2 , and F - , and the results are compared with corresponding full CI results

Second-order perturbation theory with a CASSCF reference function

An MCSCF method based on a restricted active space (RAS) type wave function has been implemented. The RAS concept is an extension of the complete active space (CAS) formalism, where the active orbitals are partitioned into three subspaces: RAS1, which contains up to a given maximum number of hole; RAS2, where all possible distributions of electrons are allowed; and RAS3, which contains up to a given maximum number of electrons. A typical example of a RAS wave function is all single, double, etc. excitations with a CAS reference space. Spin-adapted configurations are used as the basis for the MC expansion

The restricted active space self-consistent-field method, implemented with a split graph unitary group approach

The lower excited states for the molecules aminobenzonitrile (ABN) and (dimethylamino)benzonitrile (DMABN) have been studied as a function of the twisting and wagging motion of the amino group. Theoretical calculations have been performed using the complete active space (GAS) SCF method in combination with multiconfigurational second Order perturbation theory (CASPT2): Basis sets of the ANO-type (C,N/3s2p1d and H/2s) were employed. Ground state geometries were optimized at the CASSCF level. The excitation energies were computed as function of a twist angle, where the amino group is rotated with respect to the benzonitrile plane, and for two values of the wagging angle (0 and 21 degrees). The influence of the wagging angle in the nontwisted molecules was also analyzed. The results fully confirm the twist intramolecular charge transfer (TICT) model proposed to explain the dual fluorescence phenomena occurring in DMABN. The absence of the low frequency part of the fluorescence spectrum in ABN in explained by the shape of the potential energy surface along the isomerization path, due to the large energy gaps among the interacting states, which prevents the amino group from rotating into the TICT state. Calculated transition energies (absorption and emission), structural, and electrical properties of the ground and excited states are in agreement with available experimental information.

Theoretical study of the internal charge transfer in aminobenzonitriles

Theoretical Study of the Electronic Spectra of Uracil and Thymine

The electronic spectra of the title molecules have been studied using a newly proposed quantum chemical approach for ab initio calculations of dynamic electron correlation effects in molecular systems: multiconfigurational second-order perturbation theory (CASPT2). For cyclopentadiene and furan, the calculations comprise three valence excited singlet states and, in addition, the la2 - 3s, 3p, and 3d Rydberg states, thus providing a full assignment of the spectra in the energy range below 8.0 eV. For pyrrole, the 2bl - 3s. 3p, and 3d components of the Rydberg series have been added. The four lowest triplet states have also been studied in all three molecules. The computed excitation energies deviate from experiment by less than 0.17 eV in all cases where an assignment is possible. It is shown that the two main features in the spectra are caused by the valence excited states 1Bz (5.27, 5.92,6.04 eV) and 'A: (7.89, 7.46, 7.74 eV), where the calculated energies for the two states in the three molecules are given in parentheses. In addition, the 'A; state has been determined to appear near 6 eV in all three molecules. These results differ drastically from earlier theoretical predictions but are in agreement with experimental data. A number of new assignments of the Rydberg states are suggested.

Bjoern O. Roos

Papers

Second-order perturbation theory with a CASSCF reference function

The restricted active space self-consistent-field method, implemented with a split graph unitary group approach

Theoretical study of the internal charge transfer in aminobenzonitriles

Theoretical Study of the Electronic Spectra of Uracil and Thymine

Theoretical Study of the Electronic Spectra of Cyclopentadiene, Pyrrole, and Furan