TY - JOUR
T1 - Relativistic and correlated all-electron calculations on the ground and excited states of AgH and AuH
AU - Witek, Henryk A.
AU - Nakijima, Takahito
AU - Hirao, Kimihiko
PY - 2000/11/8
Y1 - 2000/11/8
N2 - We report relativistic all-electron multireference based perturbation calculations on the low-lying
excited states of gold and silver hydrides. For AuH, we consider all molecular states dissociating to
the Au(2S)1H(2S) and Au(2D)1H(2S) atomic limits, and for AgH, the states corresponding to the
Ag(2S)1H(2S), Ag(2P)1H(2S), and Ag(2D)1H(2S) dissociation channels. Spin-free relativistic
effects and the correlation effects are treated on the same footing through the relativistic scheme of
eliminating small components ~RESC!. Spin–orbit effects are included perturbatively. The
calculated potential energy curves for AgH are the first reported in the literature. The computed
spectroscopic properties agree well with experimental findings; however, the assignment of states
does not correspond to our calculations. Therefore, we give a reinterpretation of the experimentally
observed C 1P, a 3P, B 1S1, b(3D1)1, D 1P, c1
3
P1 , and c0(3P0) states. A labeling suggested by
us is a1, C01, b02, c2, B3P01, d3P1 , e1, f 1 and g1, respectively. The spin–orbit states
corresponding to Ag(2D)1H(2S) have not well defined the L and S quantum numbers, and
therefore, they probably correspond to Hund’s coupling case c. For AuH, we present a comparison
of the calculated potential energy curves and spectroscopic parameters with the previous
configuration interaction study and the experiment.
AB - We report relativistic all-electron multireference based perturbation calculations on the low-lying
excited states of gold and silver hydrides. For AuH, we consider all molecular states dissociating to
the Au(2S)1H(2S) and Au(2D)1H(2S) atomic limits, and for AgH, the states corresponding to the
Ag(2S)1H(2S), Ag(2P)1H(2S), and Ag(2D)1H(2S) dissociation channels. Spin-free relativistic
effects and the correlation effects are treated on the same footing through the relativistic scheme of
eliminating small components ~RESC!. Spin–orbit effects are included perturbatively. The
calculated potential energy curves for AgH are the first reported in the literature. The computed
spectroscopic properties agree well with experimental findings; however, the assignment of states
does not correspond to our calculations. Therefore, we give a reinterpretation of the experimentally
observed C 1P, a 3P, B 1S1, b(3D1)1, D 1P, c1
3
P1 , and c0(3P0) states. A labeling suggested by
us is a1, C01, b02, c2, B3P01, d3P1 , e1, f 1 and g1, respectively. The spin–orbit states
corresponding to Ag(2D)1H(2S) have not well defined the L and S quantum numbers, and
therefore, they probably correspond to Hund’s coupling case c. For AuH, we present a comparison
of the calculated potential energy curves and spectroscopic parameters with the previous
configuration interaction study and the experiment.
UR - http://www.scopus.com/inward/record.url?scp=0034321296&partnerID=8YFLogxK
U2 - 10.1063/1.1308554
DO - 10.1063/1.1308554
M3 - Article
AN - SCOPUS:0034321296
VL - 113
SP - 8015
EP - 8025
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 18
ER -