862 research outputs found
The electronic structure of pyrazine. Configuration interaction calculations using an extended basis
Extensive ab initio double zeta basis set configuration interaction calculations have been carried out on the nπ^∗ and ππ^∗ states of pyrazine as well as on the low‐lying n and π cations. The calculations corroborate the validity of the valence bond (VB) model for the interaction of lone pair excitations proposed earlier by Wadt and Goddard. Good agreement (errors of ∼0.2 eV) with experiment is obtained (except for the higher‐lying 1ππ∗ states that possess significant ionic character). The calculations indicate that the order of increasing ionization potentials is ^2A_g(n), 2B_(1g)(π), 2B_(1u)(n), and ^2B_(2g)(π). The forbidden 1 ^1B_(2g)(nπ^∗) state is predicted to be 1.30 eV above the allowed 1^ 1B_(3u)(nπ^∗) state. Finally, the calculations indicate that the adiabatic excitation energies to the 1^ 3B_1(nπ^∗) and 1^ 3A_1(ππ^∗) states in pyridine should be nearly degenerate at ∼3.6 eV
One-Electron Ionization of Multielectron Systems in Strong Nonresonant Laser Fields
We present a novel approach to calculating strong field ionization dynamics
of multielectron molecular targets. Adopting a multielectron wavefunction
ansatz based on field-free ab initio neutral and ionic multielectron states, a
set of coupled time-dependent single-particle Schroedinger equations describing
the neutral amplitude and continuum electron are constructed. These equations,
amenable to direct numerical solution or further analytical treatment, allow
one to study multielectron effects during strong field ionization, recollision,
and high harmonic generation. We apply the method to strong field ionization of
CO_2, and suggest the importance of intermediate core excitation to explain
previous failure of analytical models to reproduce experimental ionization
yields for this molecule.Comment: 25 pages, 6 figure
Mechanisms of two-color laser-induced field-free molecular orientation
Two mechanisms of two-color (\omega + 2\omega) laser-induced field-free
molecular orientation, based on the hyperpolarizability and ionization
depletion, are explored and compared. The CO molecule is used as a
computational example. While the hyperpolarizability mechanism generates small
amounts of orientation at intensities below the ionization threshold,
ionization depletion quickly becomes the dominant mechanism as soon as ionizing
intensities are reached. Only the ionization mechanism leads to substantial
orientation (e.g. on the order of || > 0.1). For intensities typical
of laser-induced molecular alignment and orientation experiments, the two
mechanism lead to robust, characteristic timings of the field-free orientation
wave-packet revivals relative to the the alignment revivals and the revival
time. The revival timings can be used to detect the active orientation
mechanism experimentally
Creation of Rydberg Polarons in a Bose Gas
We report spectroscopic observation of Rydberg polarons in an atomic Bose
gas. Polarons are created by excitation of Rydberg atoms as impurities in a
strontium Bose-Einstein condensate. They are distinguished from previously
studied polarons by macroscopic occupation of bound molecular states that arise
from scattering of the weakly bound Rydberg electron from ground-state atoms.
The absence of a -wave resonance in the low-energy electron-atom scattering
in Sr introduces a universal behavior in the Rydberg spectral lineshape and in
scaling of the spectral width (narrowing) with the Rydberg principal quantum
number, . Spectral features are described with a functional determinant
approach (FDA) that solves an extended Fr\"{o}hlich Hamiltonian for a mobile
impurity in a Bose gas. Excited states of polyatomic Rydberg molecules
(trimers, tetrameters, and pentamers) are experimentally resolved and
accurately reproduced with FDA.Comment: 5 pages, 3 figure
Theory of excitation of Rydberg polarons in an atomic quantum gas
We present a quantum many-body description of the excitation spectrum of
Rydberg polarons in a Bose gas. The many-body Hamiltonian is solved with
functional determinant theory, and we extend this technique to describe Rydberg
polarons of finite mass. Mean-field and classical descriptions of the spectrum
are derived as approximations of the many-body theory. The various approaches
are applied to experimental observations of polarons created by excitation of
Rydberg atoms in a strontium Bose-Einstein condensate.Comment: 14 pages, 9 figures. arXiv admin note: substantial text overlap with
arXiv:1706.0371
Resolving a puzzling anomaly in the spin-coupled generalized valence bond description of benzene
In an earlier study of benzene, Small and Head-Gordon found that the spin-coupled generalized valence bond (SCGVB) wave function for the π system predicted a distorted (non-D6h) geometry, one with alternating CC bond lengths. However, the variations in the energy were very small and the predictions were made using a very small basis set (STO-3G). We re-examined this prediction using a much larger basis set (aug-cc-pVTZ) to determine the dependence of the energy of benzene on the distortion angle, ΔθCXC (ΔθCXC = 0° corresponds to the D6h structure). We also found a distorted geometry with the optimum ΔθCXC being 0.31° with an energy 0.040 kcal mol⁻¹ lower than that for the D6h structure. In the optimum geometry, adjacent CC bond lengths are 1.3861 Å and 1.4004 Å. Analysis of the SCGVB wave function led us to conclude that the cause of the unusual non-D6h geometry predicted by the SCGVB calculations seems to be a result of the interaction between the Kekulé and Dewar components of the full SCGVB wave function. The addition of doubly ionic configurations to the SCGVB wave function leads to the prediction of a D6h geometry for benzene and a dependence on ΔθCXC essentially the same as that predicted by the complete active space self-consistent field wave function
Controlling the accuracy of the density matrix renormalization group method: The Dynamical Block State Selection approach
We have applied the momentum space version of the Density Matrix
Renormalization Group method (-DMRG) in quantum chemistry in order to study
the accuracy of the algorithm in the new context. We have shown numerically
that it is possible to determine the desired accuracy of the method in advance
of the calculations by dynamically controlling the truncation error and the
number of block states using a novel protocol which we dubbed Dynamical Block
State Selection (DBSS). The relationship between the real error and truncation
error has been studied as a function of the number of orbitals and the fraction
of filled orbitals. We have calculated the ground state of the molecules
CH, HO, and F as well as the first excited state of CH. Our
largest calculations were carried out with 57 orbitals, the largest number of
block states was 1500--2000, and the largest dimensions of the Hilbert space of
the superblock configuration was 800.000--1.200.000.Comment: 12 page
Electron attachment to valence-excited CO
The possibility of electron attachment to the valence state of CO
is examined using an {\it ab initio} bound-state multireference configuration
interaction approach. The resulting resonance has symmetry;
the higher vibrational levels of this resonance state coincide with, or are
nearly coincident with, levels of the parent state. Collisional
relaxation to the lowest vibrational levels in hot plasma situations might
yield the possibility of a long-lived CO state.Comment: Revtex file + postscript file for one figur
Electron correlations for ground state properties of group IV semiconductors
Valence energies for crystalline C, Si, Ge, and Sn with diamond structure
have been determined using an ab-initio approach based on information from
cluster calculations. Correlation contributions, in particular, have been
evaluated in the coupled electron pair approximation (CEPA), by means of
increments obtained for localized bond orbitals and for pairs and triples of
such bonds. Combining these results with corresponding Hartree-Fock (HF) data,
we recover about 95 % of the experimental cohesive energies. Lattice constants
are overestimated at the HF level by about 1.5 %; correlation effects reduce
these deviations to values which are within the error bounds of this method. A
similar behavior is found for the bulk modulus: the HF values which are
significantly too high are reduced by correlation effects to about 97 % of the
experimental values.Comment: 22 pages, latex, 2 figure
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