Androutsopoulos Alexandros, Tzeli Demeter
Laboratory of Physical Chemistry, Department of Chemistry, National and Kapodistrian University of Athens Panepistimiopolis Zografou, Athens 15771, Greece.
Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, 48 Vassileos Constantinou Ave, Athens 11635, Greece.
ACS Omega. 2025 Aug 29;10(35):40174-40189. doi: 10.1021/acsomega.5c05197. eCollection 2025 Sep 9.
In the present work, the ground state as well as some excited states of the MoX diatomic molecules, where X = Li, Be, B, C, N, O, and F, have been investigated to shed light on the nature of their chemical bonding. To this end, density functional theory, multireference configuration interaction and coupled-cluster methodologies have been employed in conjunction with aug-cc-pV5Z-(-PP) and aug-cc-pwCV5Z-(-PP) basis sets. Dissociation energies, dipole moments, and various spectroscopic constants are calculated with a view to studying the impact of the gradual increase of the number of valence electrons of X atom moving across the second period of the periodic table on the calculated properties of MoX. The Mo atom is a versatile atom forming different types of chemical bonds. The bonds formed in MoX range from a half bond (MoBe) to a quadruple bond (MoC), while all types of bonds are observed, including dative, covalent, and ionic. The corresponding dissociation energies range from 14.4 to 149.2 (152.5; CBS limit) kcal/mol at the C-MRCISD+Q and C-RCCSD-(T)/aug-cc-pV5Z-(-PP) levels. Finally, to evaluate the bond strength of the ground states, it was found that the dissociation energy per bond value is ∼ 25 kcal/mol for MoLi, MoBe and MoB, ∼ 40 kcal/mol for MoC and MoN, 61 kcal/mol for MoO and 111 kcal/mol for MoF which forms an ionic bond.
在本工作中，对MoX双原子分子（其中X = Li、Be、B、C、N、O和F）的基态以及一些激发态进行了研究，以阐明其化学键的本质。为此，结合aug-cc-pV5Z-(-PP)和aug-cc-pwCV5Z-(-PP)基组，采用了密度泛函理论、多参考组态相互作用和耦合簇方法。计算了离解能、偶极矩和各种光谱常数，以研究X原子价电子数在元素周期表第二周期中逐渐增加对MoX计算性质的影响。Mo原子是一种能形成不同类型化学键的多功能原子。MoX中形成的键从半键（MoBe）到四重键（MoC）不等，同时观察到了所有类型的键，包括配位键、共价键和离子键。在C-MRCISD+Q和C-RCCSD-(T)/aug-cc-pV5Z-(-PP)水平下，相应的离解能范围为14.4至149.2（152.5；CBS极限）kcal/mol。最后，为了评估基态的键强度，发现MoLi、MoBe和MoB的每个键的离解能值约为25 kcal/mol，MoC和MoN为40 kcal/mol，MoO为61 kcal/mol，形成离子键的MoF为111 kcal/mol。
