Electronic Structure of the Ground and Low-Lying States of MoLi
Molybdenum lithium compounds and materials are being researched and applied in cutting-edge industries; however, their bonding has not been explored in a systematic way. The present study investigates the MoLi molecule, to shed light on its bonding. Specifically, the electronic structure and bonding...
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| Main Authors: | , |
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| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2025-07-01
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| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/30/13/2874 |
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| Summary: | Molybdenum lithium compounds and materials are being researched and applied in cutting-edge industries; however, their bonding has not been explored in a systematic way. The present study investigates the MoLi molecule, to shed light on its bonding. Specifically, the electronic structure and bonding of the ground and 40 low-lying states of the MoLi molecule are explored, employing multireference methodologies, i.e., CASSCF and MRCISD(+Q) in conjunction with the aug-cc-pV5z(-PP) basis set. Bond distances, dissociation energies, dipole moments as well as common spectroscopic constants are given, while the potential energy curves are plotted. For the ground state, X<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mmultiscripts><mrow><mo>Σ</mo></mrow><mrow><mo>+</mo></mrow><none></none><mprescripts></mprescripts><none></none><mn>6</mn></mmultiscripts></mrow></semantics></math></inline-formula>, it is found that <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msub><mrow><mi>R</mi></mrow><mrow><mi mathvariant="normal">e</mi></mrow></msub></mrow></semantics></math></inline-formula> = 2.708 Å, <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msub><mrow><mi>D</mi></mrow><mrow><mi mathvariant="normal">e</mi></mrow></msub></mrow></semantics></math></inline-formula> = 24.1 kcal/mol, <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msub><mrow><mi>ω</mi></mrow><mrow><mi mathvariant="normal">e</mi></mrow></msub></mrow></semantics></math></inline-formula> = 316.8 <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msup><mrow><mi>cm</mi></mrow><mrow><mo>−</mo><mn>1</mn></mrow></msup></mrow></semantics></math></inline-formula>, <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msub><mrow><mi>ω</mi></mrow><mrow><mi mathvariant="normal">e</mi></mrow></msub><msub><mrow><mi>x</mi></mrow><mrow><mi mathvariant="normal">e</mi></mrow></msub></mrow></semantics></math></inline-formula> = 2.11 <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msup><mrow><mi>cm</mi></mrow><mrow><mo>−</mo><mn>1</mn></mrow></msup></mrow></semantics></math></inline-formula>, and <i>μ</i> = 3.63 D. Overall, the calculated states present a variety of bonds, from weak van der Waals up to the formation of 2.5 bonds. The dissociation energies of the calculated states range from 2.3 kcal/mol (<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi mathvariant="normal">a</mi><mmultiscripts><mrow><msup><mrow><mo>Σ</mo></mrow><mrow><mo>+</mo></mrow></msup></mrow><none></none><none></none><mprescripts></mprescripts><none></none><mrow><mn>8</mn></mrow></mmultiscripts></mrow></semantics></math></inline-formula>) to 34.7 (<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi mathvariant="normal">c</mi><mmultiscripts><mrow><mo>Π</mo></mrow><none></none><none></none><mprescripts></mprescripts><none></none><mrow><mn>4</mn></mrow></mmultiscripts></mrow></semantics></math></inline-formula>), while the bond distances range from 2.513 Å to 3.354 Å. Finally, dipole moment values up to 3.72 D are calculated. In most states, a 2s<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msub><mrow><mrow><mn>2</mn><mi mathvariant="normal">p</mi></mrow></mrow><mrow><mi mathvariant="normal">z</mi></mrow></msub></mrow></semantics></math></inline-formula> hybridization on Li and a <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msub><mrow><mrow><mn>4</mn><mi mathvariant="normal">d</mi></mrow></mrow><mrow><msup><mrow><mi mathvariant="normal">z</mi></mrow><mrow><mn>2</mn></mrow></msup></mrow></msub></mrow></semantics></math></inline-formula>5s<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msub><mrow><mrow><mn>5</mn><mi mathvariant="normal">p</mi></mrow></mrow><mrow><mi mathvariant="normal">z</mi></mrow></msub></mrow></semantics></math></inline-formula> or 5s<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msub><mrow><mrow><mn>5</mn><mi mathvariant="normal">p</mi></mrow></mrow><mrow><mi mathvariant="normal">z</mi></mrow></msub></mrow></semantics></math></inline-formula> hybridization on Mo are found. Moreover, it is observed that the excited Li(<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mmultiscripts><mrow><mi mathvariant="normal">P</mi></mrow><none></none><none></none><mprescripts></mprescripts><none></none><mrow><mn>2</mn></mrow></mmultiscripts></mrow></semantics></math></inline-formula>) atom forms the shortest bonds because its empty <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msup><mrow><mrow><mn>2</mn><mi mathvariant="normal">s</mi></mrow></mrow><mrow><mn>0</mn></mrow></msup></mrow></semantics></math></inline-formula> orbital can easily accept electrons, resulting in a strong σ dative bond. Finally, the present work highlights the exceptional ability of lithium atoms to participate in a variety of bonding schemes, and it could provide the opening gate for further investigation of this species or associated material and complexes. |
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| ISSN: | 1420-3049 |