Electronic States of Al₃P₂, Al₂P₃, and Their Ions

Abstract

Complete active-space self-consistent field (CASSCF) method followed by multireference singles + doubles configuration interaction (MRSDCI) calculations that included up to 4 million configurations were carried out on the electronic states of Al 3 P 2 , Al 2 P 3 and their anions and cations. Our computed results explain the recently reported anion photoelectron spectra of Al 2 P 3and Al 3 P 2by Neumark and co-workers. 1 We find that both the Al 2 P 3and Al 2 P 3 species have D 3h undistorted trigonal bipyramidal structures consistent with the sharp and intense ground-state peak in the observed spectra. But the neutral Al 3 P 2 cluster was found to be Jahn-Teller distorted in contrast to the Al 3 P 2anion, which has a D 3h undistorted trigonal bipyramidal structure, consistent with the observed extended vibrational progression of the X state of the spectra. Our computed electron affinities agree well with the onsets of the observed X peaks in both spectra. We assign the partially resolved vibrational structure in the observed spectra to the totally symmetric stretch mode than to symmetry lowering of Al 2 P 3 , which is found to be in a 2 A 2 ′′ (D 3h ) state and cannot undergo Jahn-Teller distortion. Seven electronic states of Al 3 P 2 are computed, among which the 2 A 1 (C 2V ) state is the ground state with a distorted trigonal bipyramid structure. The distorted 2 A 1 and 2 B 1 (C 2V ) states are identified as Jahn-Teller components of the undistorted 2 E′ and 2 E′′ (D 3h ) states, respectively. Properties of four electronic states of Al 2 P 3 , Al 3 P 2 + , and Al 2 P 3 + are also reported. The ground states of both Al 3 P 2 + and Al 2 P 3 + are undistorted 3 A 2 ′ and 1 A 1 ′, respectively (D 3h symmetry). The atomization energy, adiabatic ionization potentials, dipole moments, and other properties for the electronic states of Al 3 P 2 and Al 2 P 3 are calculated and discussed. Comparisons are made with the Ga and In analogues of these species.

Evolution of the electronic structure and properties of neutral and charged aluminum phosphide clusters: A comprehensive analysis

“…Gomez et al [7] reported the experimental adiabatic electron affinity and vertical detachment energy of Al m P n . The theoretical prediction of Al m P n electron detachment energy and electron affinities is found in the 2000-2002 study of Archibong et al [11,12,20] and Balasubramanian and Feng [15]. The objective of the present study is to study the evolution of cluster properties (such as atomic structure, coordination number, interatomic distance, binding energy, relative stability, and electronic properties) with size.…”

“…I see from Fig. 9 that the HOMO-LUMO gaps in neutral clusters are particularly large for AlP, (AlP) 9 , (AlP) 12 , and (AlP) 15 . I see from Fig.…”

“…This cutoff was arrived at by examining all the interatomic distances in the clusters studied and by noting that there was a distinct gap in these distances beyond 2.9 Å. In (AlP) 6 to (AlP) 15 respectively. In Fig.…”

“…Archibong et al [11,12] have reported the equilibrium geometries, harmonic vibrational frequencies and electron detachment energies of the neutral and anion AlP 2 , Al 2 P 2 , Al 3 P, and AlP 3 performed at density functional theory (B3LYP, BP86, and BPW91-DFT) and ab initio methods [MP2 and CCSD (T)]. Feng and Balasubramanian [13][14][15] have also studied the structures and potential energy curves of a number of elec-E-mail address: gl-guoling@163.com. tronic states of Al 3 P, AlP 3 and its positive ions, Al 2 P 3 , Al 3 P 2 and their ions using the complete active space self-consistent field (CASSCF) method followed by multireference singles and doubles configuration interaction (MRSDCI), and found the C 3v structure to be the global minima of AlP 3 , which is different from Archibong et al [12] prediction.…”

Origins of Stability in Mixed Bismuth−Indium Clusters

“…Al x P y , B x N y , Ga x P y , , Ga x As y , In x P y , and Bi 3 Ga y . Complementing the experimental studies are several theoretical studies that have expanded knowledge of the geometric and electronic properties of these clusters. ,− …”