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