Diabatic valence-hole states in the C$_2$ molecule: 'Putting Humpty Dumpty together again'

التفاصيل البيبلوغرافية
العنوان: Diabatic valence-hole states in the C$_2$ molecule: 'Putting Humpty Dumpty together again'
المؤلفون: Jiang, Jun, Ye, Hong-Zhou, Nauta, Klaas, Van Voorhis, Troy, Schmidt, Timothy W., Field, Robert W.
سنة النشر: 2022
المجموعة: Physics (Other)
مصطلحات موضوعية: Physics - Chemical Physics
الوصف: Despite the long history of spectroscopic studies of the C$_2$ molecule, fundamental questions about its chemical bonding are still being hotly debated. The complex electronic structure of C$_2$ is a consequence of its dense manifold of near-degenerate, low-lying electronic states. A global multi-state diabatic model is proposed here to disentangle the numerous configuration interactions within four symmetry manifolds of C$_2$ ($^{1}\Pi_g$, $^{3}\Pi_g$, $^{1}\Sigma_u^+$, and $^{3}\Sigma_u^+$). The key concept of our model is the existence of two "valence-hole" configurations, $2\sigma_g^22\sigma_u^11\pi_{u}^33\sigma_g^2$ for $^{1,3}\Pi_g$ states and $2\sigma_g^22\sigma_u^11\pi_{u}^43\sigma_g^1$ for $^{1,3}\Sigma_u^+$ states that derive from $3\sigma_g\leftarrow2\sigma_u$ electron promotion. The lowest-energy state from each of the four C$_2$ symmetry species is dominated by this type of valence-hole configuration at its equilibrium internuclear separation. As a result of their large binding energy (nominal bond order of 3) and correlation with the 2s$^2$2p$^2$+2s2p$^3$ separated-atom configurations, the presence of these valence-hole configurations has a profound impact on the $global$ electronic structure and unimolecular dynamics of C$_2$.
نوع الوثيقة: Working Paper
DOI: 10.1021/acs.jpca.2c00495
URL الوصول: http://arxiv.org/abs/2203.03138
رقم الأكسشن: edsarx.2203.03138
قاعدة البيانات: arXiv
الوصف
DOI:10.1021/acs.jpca.2c00495