First observation and electronic structure of the diatomic platinum nitride molecule

Friedman-Hill, E. J.; Field, R. W.
May 1994
Journal of Chemical Physics;5/1/1994, Vol. 100 Issue 9, p6141
Academic Journal
The optical spectrum of the PtN radical has been observed directly for the first time. The strongest band system [(0,0) bandhead at 18 591 cm-1] displays an unusual ‘‘perpendicular ΔΩ=0’’ perturbation which gives rise to strong intensity cancellation effects. Although a 4Σ- ground state was expected for PtN, we have assigned the ground state as 2Πr; a 4Σ- assignment is not consistent with our observations. We have used arguments based on both molecular orbital theory and atomic-ion-in-molecule theory to explain the observed ground state symmetry in light of the observed hyperfine structure. Four electronic bands involving a total of six Hund’s case (c) |v,Ω> substrates have been rotationally analyzed, and many more bands have been observed at lower resolution. The ground state was found to have Ω=0.5 and its principal constants are Be=0.455 708(5) cm-1, αe=0.003 448 1(1) cm-1, spin–rotation constant γ0=0.061 26(7) cm-1, ωe=947.0(5) cm-1, and ωexe=5.0(5) cm-1. Two other Ω states were observed at low energies—an Ω=1.5 state at Te=2 985.665(2) cm-1, with B0=0.445 233(8) cm-1, q=1.522(5)×10-6 cm-1, ωe=901(1) cm-1, and ωexe=8(1) cm-1, and another Ω=0.5 state with Te undetermined and other constants remarkably similar to those of the ground state (B0=0.453 07(6) cm-1, γ0=0.062 02(4) cm-1, ωe=947(1) cm-1, and ωexe=5(1) cm-1).


Related Articles

  • Using effective operators in calculating the hyperfine structure of atoms. Dzuba, V. A.; Flambaum, V. V.; Kozlov, M. G.; Porsev, S. G. // Journal of Experimental & Theoretical Physics;Nov98, Vol. 87 Issue 5, p885 

    We propose a method for calculating the hyperfine structure (hfs) of multielectron atoms based on a combination of configuration superposition and many-body perturbation theory. The latter is used to construct an effective Hamiltonian and an effective hfs operator in configurational space. The...

  • Electronic coupling calculation and pathway analysis of electron transfer reaction using ab initio fragment-based method. I. FMO-LCMO approach. Nishioka, Hirotaka; Ando, Koji // Journal of Chemical Physics;5/31/2011, Vol. 134 Issue 20, p204109 

    By making use of an ab initio fragment-based electronic structure method, fragment molecular orbital-linear combination of MOs of the fragments (FMO-LCMO), developed by Tsuneyuki et al. [Chem. Phys. Lett. 476, 104 (2009)], we propose a novel approach to describe long-distance electron transfer...

  • Self-Consistent Solutions for the Scattering State with Two Free Electrons. Hahn, Y. K.; Gau, J. N.; Zerrad, E. // Few-Body Systems;Nov2013, Vol. 54 Issue 11, p1781 

    Wave functions for the scattering states with two free electrons in the field of an ion core are explicitly calculated by the self-consistent, continuum Hartree–Fock (CHF) theory. Typically, such states are associated with the three-body recombination, collisional ionization and...

  • Analytic energy gradients with frozen molecular orbitals in coupled-cluster and many-body... Baeck, Kyoung K.; Watts, John D.; Bartlett, Rodney J. // Journal of Chemical Physics;9/8/1997, Vol. 107 Issue 10, p3853 

    Reports on the systematic study of the magnitude and trends of the effects of frozen molecular orbitals in coupled-cluster and many-body perturbation theory methods. Theoretical considerations and implementations; Effects of core correlation on geometry and vibrational frequencies.

  • Vibrational analyses of trans-polyacetylene based on ab initio second-order Mo\ller–Plesset perturbation calculations of trans-oligoenes. Hirata, So; Torii, Hajime; Tasumi, Mitsuo // Journal of Chemical Physics;11/22/1995, Vol. 103 Issue 20, p8964 

    Structures and vibrational force fields of all-trans-oligoenes of various chain lengths are studied by ab initio molecular orbital (MO) calculations at the second-order Mo\ller–Plesset perturbation (MP2) level with the 3-21G and 6-31G* basis sets. Dependencies of the structure parameters...

  • Coupled-cluster study of the electronic structure and energetics of tetrasulfur, S4. Matus, Myrna H.; Dixon, David A.; Peterson, Kirk A.; Harkless, John A. W.; Francisco, Joseph S. // Journal of Chemical Physics;11/7/2007, Vol. 127 Issue 17, p174305 

    Ab initio electronic structure calculations are reported for S4. Geometric and energetic parameters are calculated using the singles and doubles coupled-cluster method, including a perturbutional correction for connected triple excitation, CCSD(T), together with systematic sequences of...

  • An investigation of three-body effects in intermolecular forces. III. Far infrared laser vibration–rotation–tunneling spectroscopy of the lowest internal rotor states of Ar2HCl. Elrod, M. J.; Loeser, J. G.; Saykally, R. J. // Journal of Chemical Physics;4/1/1993, Vol. 98 Issue 7, p5352 

    The c-type intermolecular out-of-plane bend of Ar2HCl has been observed at 45.2 cm-1, completing the high resolution far infrared measurements of the three lowest-lying Ar2HCl bending states which correlate to the j=1 internal rotational state of the HCl monomer. The rotational and nuclear...

  • Hyperfine structures of the triplet states of 23Na85Rb. Matsubara, Kensuke; Wang, You-Chang; Ishikawa, Kiyoshi; Baba, Masaaki; McCaffery, Anthony J.; Katô, Hajime // Journal of Chemical Physics;10/1/1993, Vol. 99 Issue 7, p5036 

    The sub-Doppler high resolution excitation spectrum of NaRb was measured by selectively monitoring the fluorescence intensity from perturbed levels to the (1)3Σ+ lower state. Many transitions were observed to the (2)3Σ+ state perturbed by B 1Π. Energy shifts of the perturbed levels were...

  • Nonorthogonal localized molecular orbitals in electronic structure theory. Liu, Shubin; Pérez-Jordá, José M.; Yang, Weitao // Journal of Chemical Physics;1/22/2000, Vol. 112 Issue 4 

    The concept of nonorthogonal localized molecular orbital (NOLMO) is investigated in this paper. Given a set of the commonly used canonical molecular orbitals, a direct minimization algorithm is proposed to obtain both the orthogonal localized molecular orbitals (OLMO) and NOLMO by using the Boys...


Read the Article


Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics