Quadruple Bonding in the Ground and Low-Lying Excited States of the Diatomic Molecules TcN, RuC, RhB, and PdBe

被引:15
作者
Tzeli, Demeter [1 ,2 ]
Karapetsas, Ioannis [1 ]
机构
[1] Natl & Kapodistrian Universi Athens, Lab Phys Chem, Dept Chem, Athens 15784, Greece
[2] Natl Hellen Res Fdn, Theoret & Phys Chem Inst, Athens 11635, Greece
关键词
ELECTRIC-DIPOLE MOMENTS; RUTHENIUM MONOCARBIDE; IRON MONOCARBIDE; BASIS-SETS; SPECTROSCOPY; C-2; TRANSITION; ATOMS; SPECTRUM; CARBIDE;
D O I
10.1021/acs.jpca.0c03208
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Multiple bonds between atoms are one of the most fundamental aspects of chemistry. Double and triple bonds are quite common, while quadruple bonds are a true oddity and very rare for the main group elements. Identifying molecules containing quadruple bonds is very important and, even more so, determining the necessary requirements for the existence of such bonds. Here we present high-level theoretical calculations on the isoelectronic MX molecules, i.e., TcN, RuC, RhB, and PdBe, showing that such a quadruple bond with main group elements is not that uncommon. We found that quadruple bonds are formed in their ground states X-3 Delta (TcN) and X-1 Sigma(+) (RuC, RhB, and PdBe) and in the two lowest excited states of TcN (1 Sigma(+), (1)Delta), RuC ((1,3)Delta), and RhB ((1,3)Delta). The quadruple bonds consist of two pi and two sigma bonds: (4d(xz)-2p(x))(2), (44(yz)-2p(y))(2), (4d(z)2-2p(z))(2), and 5s(0) <- 2s(2) (1 Sigma(+)) or 5p(z)(0) <- 2s(2) ((1,3)Delta). Bond lengths, dissociation energies, dipole moments, spectroscopic parameters, and relative energy ordering of the states were calculated via multireference and coupled cluster methodology using the aug-cc-pV5Z(X)(-PP)(M) basis sets. We study how the atomic states involved and how the gradual transition from covalent to dative bond, from TcN to PdBe, influence all of the calculated data, such as bond dissociation energies, bond lengths, and relative energy ordering of the states. Finally, we report the requirements for the occurrence of such bonds in molecular systems. All Be, B, C, and N atoms combining with the appropriate second-row transition metal can form quadruple bonds, while they cannot form such bonds with the first-row transition metals.
引用
收藏
页码:6667 / 6681
页数:15
相关论文
共 50 条
[41]   Electric properties of the low-lying excited states of benzonitrile: geometry relaxation and solvent effects [J].
Medved', Miroslav ;
Budzak, Simon ;
Pluta, Tadeusz .
THEORETICAL CHEMISTRY ACCOUNTS, 2015, 134 (06)
[42]   Structural Optimization by Quantum Monte Carlo: Investigating the Low-Lying Excited States of Ethylene [J].
Barborini, Matteo ;
Sorella, Sandro ;
Guidoni, Leonardo .
JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 2012, 8 (04) :1260-1269
[43]   Investigation of low-lying excited states in 214Po and 214Bi [J].
Esmaylzadeh, A. ;
Ley, M. ;
Blazhev, A. ;
Fransen, C. ;
Jolie, J. ;
Karayonchev, V. ;
Knafla, L. ;
Lakenbrink, C. -D. ;
Pfeil, A. ;
von Spee, F. .
PHYSICAL REVIEW C, 2024, 110 (03)
[44]   Theoretical Studies on the Low-Lying Excited States of Aluminum Cyanide (AICN) and Its Ions [J].
Liu Yuejie ;
Zhao Zengxia ;
Song Mingxing ;
Zhang Hongxing ;
Sun Chiachung .
ACTA CHIMICA SINICA, 2010, 68 (17) :1687-1691
[45]   The spectroscopic properties of the low-lying excited states and laser cooling scheme of SrBr molecule [J].
Liu, Li ;
Yang, Chuan-Lu ;
Wang, Mei-Shan ;
Ma, Xiao-Guang ;
Sun, Zhao-Peng .
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY, 2020, 228
[46]   Quantum Monte Carlo study of the ground state and low-lying excited states of the scandium dimer (vol 128, 194315, 2008) [J].
Matxain, Jon M. ;
Rezabal, Elixabete ;
Lopez, Xabier ;
Ugalde, Jesus M. ;
Gagliardi, Laura .
JOURNAL OF CHEMICAL PHYSICS, 2010, 132 (13)
[48]   Quadruple bonds in MoC: Accurate calculations and precise measurement of the dissociation energy of low-lying states of MoC [J].
Androutsopoulos, Alexandros ;
Tzeli, Demeter ;
Tomchak, Kimberly H. ;
Morse, Michael D. .
JOURNAL OF CHEMICAL PHYSICS, 2024, 160 (23)
[49]   Low-lying electronic terms of diatomic molecules AB (A = Sc-Ni, B = Cu/Ag/Au) [J].
Sanati, Davood Alizadeh ;
Andrae, Dirk .
MOLECULAR PHYSICS, 2020, 118 (21-22)
[50]   Ab initio calculation on the potential energy curves and spectroscopic properties of the low-lying excited states of BCl+ [J].
Yu Kun ;
Zhang Xiao-Mei ;
Liu Yu-Fang .
ACTA PHYSICA SINICA, 2013, 62 (06)