139 research outputs found
R-matrix calculation of electron collisions with electronically excited O2 molecules
Low-energy electron collisions with O molecules are studied using the
fixed-bond R-matrix method. In addition to the O ground
state, integrated cross sections are calculated for elecron collisions with the
and excited states of O molecules. 13
target electronic states of O are included in the model within a valence
configuration interaction representations of the target states. Elastic cross
sections for the and excited states are
similar to the cross sections for the ground state. As in
case of excitation from the state, the O
resonance makes the dominant contribution to excitation cross sections from the
and states. The magnitude of excitation
cross sections from the state to the
state is about 10 time larger than the corresponding cross sections from the
to the state. For this
transition, our cross section at
4.5 eV agrees well with the available experimental value. These results should
be important for models of plasma discharge chemistry which often requires
cross sections between the excited electronic states of O.Comment: 26 pages, 10 figure
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
The Dipole Moments and Molar Refractions of Several Trans-Beta-Nitrostyrenes
The dipole moments and molar refractions are reported for p-nitrostyrene (4.24 D, 44.3 ml.), trans-betanitrostyrene (4.50 D, 45.7 ml.), the p-methoxy (5.45 D, 56.3 ml.), p-methyl (4.97 D, 52.0 ml.), p-fluoro (3-12 D, 45.5ml), p-chloro (2.90 D, 51.8 ml.), p-bromo (3.02 D, 54.4 ml.), p-iodo (3.26 D, 58.0 ml.), p-nitro (0.83 D, 52.0 ml.), and p-cyano 0.96 D, 47.9 ml.) derivatives of trans-beta-nitrostyrene. It is suggested that the large dipole moments obtained for the p-nitro and p-cyano-beta-nitrostyrenes may be due to unusually large atomic polarizations which would not be taken into consideration by the present method of measurement and calculation
Towards the electron EDM search: Theoretical study of HfF+
We report first ab initio relativistic correlation calculations of potential
curves for ten low-lying electronic states, effective electric field on the
electron and hyperfine constants for the ^3\Delta_1 state of cation of a heavy
transition metal fluoride, HfF^+, that is suggested to be used as the working
state in experiments to search for the electric dipole moment of the electron.
It is shown that HfF^+ has deeply bound ^1\Sigma^+ ground state, its
dissociation energy is D_e=6.4 eV. The ^3\Delta_1 state is obtained to be the
relatively long-lived first excited state lying about 0.2 eV higher. The
calculated effective electric field E_eff=W_d|\Omega| acting on an electron in
this state is 5.84*10^{24}Hz/(e*cm)Comment: 4 page
Configuration interaction calculation of hyperfine and P,T-odd constants on ^{207}PbO excited states for the electron EDM experiments
We report first configuration interaction calculations of hyperfine constants
A_\parallel and the effective electric field W_d acting on the electric dipole
moment of the electron, in two excited electronic states of ^{207}PbO. The
obtained hyperfine constants, A_\parallel = -3826 MHz for the a(1) state and
A_\parallel = 4887 MHz for the B(1) state, are in very good agreement with the
experimental data, -4113 MHz and 5000 \pm 200 MHz, respectively. We find W_d =
-(6.1 ^{+1.8}_{-0.6}) 10^{24} Hz/(e cm) for a(1), and W_d = (8.0 \pm 1.6)
10^{24} Hz/(e cm) for B(1). The obtained values are analyzed and compared to
recent relativistic coupled cluster results and a semiempirical estimate of W_d
for the a(1) state.Comment: 6 pages, REVTeX4 style, submitted to Pthys.Rev.
Towards the electron EDM search. Theoretical study of PbF
We report ab initio relativistic correlation calculations of potential curves
and spectroscopic constants for four lowest-lying electronic states of the lead
monofluoride. We also calculated parameters of the spin-rotational Hamiltonian
for the ground and the first excited states including P,T-odd and P-odd terms.
In particular, we have obtained hyperfine constants of the Pb nucleus.
For the state MHz, MHz and for
the A MHz, MHz. Our values of
the ground state hyperfine constants are in good agreement with the previous
theoretical studies. We discuss and explain seeming disagreement in the sign of
the constant with the recent experimental data. The effective
electric field on the electron , which is important for the planned
experiment to search for the electric dipole moment of the electron, is found
to be 3.3 * 10^{10} V/cm
Quenching of Excited Na due to He Collisions
The quenching and elastic scattering of excited Sodium by collisions with Helium have been investigated for energies between 10(exp -13) eV and 10 eV. With the ab initio adiabatic potentials and nonadiabatic radial and rotational couplings obtained from multireference single- and double-excitation configuration interaction approach, we carried out scattering calculations by the quantum-mechanical molecular-orbital close-coupling method. Cross sections for quenching reactions and elastic collisions are presented. Quenching and elastic collisional rate coefficients as a function of temperature between 1 micro-K and 10,000 K are also obtained. The results are relevant to modeling non-LTE effects on Na D absorption lines in extrasolar planets and brown dwarfs
Variational Hilbert space truncation approach to quantum Heisenberg antiferromagnets on frustrated clusters
We study the spin- Heisenberg antiferromagnet on a series of
finite-size clusters with features inspired by the fullerenes. Frustration due
to the presence of pentagonal rings makes such structures challenging in the
context of quantum Monte-Carlo methods. We use an exact diagonalization
approach combined with a truncation method in which only the most important
basis states of the Hilbert space are retained. We describe an efficient
variational method for finding an optimal truncation of a given size which
minimizes the error in the ground state energy. Ground state energies and
spin-spin correlations are obtained for clusters with up to thirty-two sites
without the need to restrict the symmetry of the structures. The results are
compared to full-space calculations and to unfrustrated structures based on the
honeycomb lattice.Comment: 22 pages and 12 Postscript figure
Ab initio coupled-cluster and configuration interaction calculations for 16-O using V_UCOM
Using the ground-state energy of 16-O obtained with the realistic V_UCOM
interaction as a test case, we present a comprehensive comparison of different
configuration interaction (CI) and coupled-cluster (CC) methods, analyzing the
intrinsic advantages and limitations of each of the approaches. In particular,
we use the importance-truncated (IT) CI and no-core shell model (NCSM) schemes
with up to 4-particle-4-hole (4p4h) excitations as well as the size extensive
CC methods with a complete treatment of one- and two-body clusters (CCSD) and a
non-iterative treatment of connected three-body clusters via the completely
renormalized correction to the CCSD energy defining the CR-CC(2,3) approach. We
discuss the impact of the center-of-mass contaminations, the choice of the
single-particle basis, and size-extensivity on the resulting energies. When the
IT-CI and IT-NCSM methods include the 4p4h excitations and when the CC
calculations include the 1p1h, 2p2h, and 3p3h clusters, as in the CR-CC(2,3)
approach, we observe an excellent agreement among the different methodologies.
This shows that despite their individual limitations, the IT-CI, IT-NCSM, and
CC methods can provide precise and consistent ab initio nuclear structure
predictions. Furthermore, the IT-CI, IT-NCSM, and CC ground-state energy values
obtained with 16-O are in good agreement with the experimental value, proving
that the V_UCOM two-body interaction allows for a realistic description of
binding energies for heavier nuclei and that all of the methods used in this
study account for most of the relevant particle correlation effects.Comment: 20 pages, 4 figures, 1 table (v2: extended version in response to
referees' comments
Recent advances in electronic structure theory and their influence on the accuracy of ab initio potential energy surfaces
Recent advances in electronic structure theory and the availability of high speed vector processors have substantially increased the accuracy of ab initio potential energy surfaces. The recently developed atomic natural orbital approach for basis set contraction has reduced both the basis set incompleteness and superposition errors in molecular calculations. Furthermore, full CI calculations can often be used to calibrate a CASSCF/MRCI approach that quantitatively accounts for the valence correlation energy. These computational advances also provide a vehicle for systematically improving the calculations and for estimating the residual error in the calculations. Calculations on selected diatomic and triatomic systems will be used to illustrate the accuracy that currently can be achieved for molecular systems. In particular, the F+H2 yields HF+H potential energy hypersurface is used to illustrate the impact of these computational advances on the calculation of potential energy surfaces
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