Journal article
A highly accurate potential energy curve for the mercury dimer
The Journal of chemical physics, Vol.132(11), pp.114301-114301-6
03/15/2010
Handle:
https://hdl.handle.net/2376/105852
PMID: 20331291
Abstract
The potential energy curve of the electronic ground state of the mercury dimer based on CCSD(T) calculations at the complete basis set (CBS) limit, including corrections for the full triples
Δ
T
and explicit spin-orbit (SO) interactions at the CCSD(T) level of theory, is presented. In the far long-range part, the potential energy curve is complemented by symmetry-adapted perturbation theory calculations. Potential curves of an analytically simple, extended Lennard-Jones form are obtained from very accurate fits to the
CBS
/
CCSD
(
T
)
+
SO
and
CBS
/
CCSD
(
T
)
+
SO
+
Δ
T
data. The
Hg
2
potential curves yield dissociation energies of
D
e
=
424
/
392
cm
−
1
and equilibrium distances of
r
e
=
3.650
/
3.679
Å
at the
CBS
/
CCSD
(
T
)
+
SO
and
CBS
/
CCSD
(
T
)
+
SO
+
Δ
T
levels of theory, respectively. By including perturbative quadruple corrections in our coupled-cluster calculations and corrections from correlating the 4f-core, we arrive at a final dissociation energy of
D
e
=
405
cm
−
1
, in excellent agreement with the experimentally estimated value of
407
cm
−
1
by Greif and Hensel. In addition, the rotational and vibrational spectroscopic constants as well as the second virial coefficient
B
(
T
)
in dependence of the temperature
T
are calculated and validated against available experimental and theoretical data.
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Details
- Title
- A highly accurate potential energy curve for the mercury dimer
- Creators
- Elke Pahl - Centre for Theoretical Chemistry and Physics, New Zealand Institute for Advanced Study, Massey University, Auckland Campus, Private Bag 102904, North Shore City, 0745 Auckland, New ZealandDetlev Figgen - Centre for Theoretical Chemistry and Physics, New Zealand Institute for Advanced Study, Massey University, Auckland Campus, Private Bag 102904, North Shore City, 0745 Auckland, New ZealandChristian Thierfelder - Centre for Theoretical Chemistry and Physics, New Zealand Institute for Advanced Study, Massey University, Auckland Campus, Private Bag 102904, North Shore City, 0745 Auckland, New ZealandKirk Peterson - Centre for Theoretical Chemistry and Physics, New Zealand Institute for Advanced Study, Massey University, Auckland Campus, Private Bag 102904, North Shore City, 0745 Auckland, New ZealandFlorent Calvo - Centre for Theoretical Chemistry and Physics, New Zealand Institute for Advanced Study, Massey University, Auckland Campus, Private Bag 102904, North Shore City, 0745 Auckland, New ZealandPeter Schwerdtfeger - Centre for Theoretical Chemistry and Physics, New Zealand Institute for Advanced Study, Massey University, Auckland Campus, Private Bag 102904, North Shore City, 0745 Auckland, New Zealand
- Publication Details
- The Journal of chemical physics, Vol.132(11), pp.114301-114301-6
- Academic Unit
- Chemistry, Department of
- Publisher
- American Institute of Physics
- Grant note
- 07-MAU-016 / UNSPECIFIED 15883VC / UNSPECIFIED
- Identifiers
- 99900546567701842
- Resource Type
- Journal article