Czernek Jirí, Zivný Oldrich
Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Heyrovsky Square 2, 162 06 Praha 6, Czech Republic.
J Chem Phys. 2008 Nov 21;129(19):194305. doi: 10.1063/1.3020764.
The multiconfigurational-reference internally contracted configuration interaction (MRCI)/aug-cc-pVQZ-based computational protocol was employed to search for the minima of the potential energy surface of the low-lying singlet and triplet electronic states of the trifluoride anion F(3) (-) in the D(infinity(h)), C(infinity(v)), C(2v), and C(s) symmetry groups. The (3)B(2) bound state was located (r(e)=1.8777 A and theta=103.39 degrees ), which was predicted to lie less than 1 eV above the X (1)Sigma(g) (+) ground state (r(e)=1.7382 A) by both the MRCI and equation-of-motion coupled-cluster singles, doubles and triples approaches [the MRCI adiabatic excitation energy extrapolated to the complete basis set (CBS) limit was 0.91 eV]. The latter value is proposed as a reliable estimate of the singlet-triplet energy gap in F(3) (-). The vertical transitions from the X (1)Sigma(g) (+) state were analyzed in terms of the reorganization of electrons leading to the excited states and the corresponding MRCI/CBS excitation energies.
采用基于多组态参考内收缩组态相互作用（MRCI）/aug-cc-pVQZ的计算方法，在(D_{\infty h})、(C_{\infty v})、(C_{2v})和(C_s)对称群中寻找三氟阴离子(F_3^-)低激发单重态和三重态电子态势能面的极小值。找到了((^3B_2))束缚态（(r_e = 1.8777 Å)，(\theta = 103.39^{\circ})），通过MRCI和运动方程耦合簇单双三重态方法预测其位于(X ^1\Sigma_g^+)基态（(r_e = 1.7382 Å)）上方不到(1 eV)处[MRCI绝热激发能外推到完全基组（CBS）极限为(0.91 eV)]。建议将后一个值作为(F_3^-)中单重态 - 三重态能隙的可靠估计。从(X ^1\Sigma_g^+)态的垂直跃迁根据导致激发态的电子重组和相应的MRCI/CBS激发能进行了分析。
