Orthogonal satellite vectors. The position of the point M is as defined by Mladenović. 36
The lowest 401 totally symmetric computed energy levels of Si2H2 relative to the dibridged ground state. (State number 401 is the trans ground state.) The states are separated by isomer: (left to right) dibridged, monobridged, vinyl, and trans.
From left to right: ground vibrational state probability densities (as functions of the angles θ1 and θ2) of the dibridged, monobridged, and disilavinylidene isomers of Si2H2 (totally symmetric states 1, 33, and 89, respectively); the computed energies of these states relative to the dibridged ground state are 0.0, 3163.6, and 4210.9 cm−1.
Probability densities (as functions of the angles θ1 and θ2) for low lying totally symmetric excited vibrational states of the dibridged, monobridged, and disilavinylidene isomers of Si2H2: (left to right) state 10, dibridged 2ν4; state 44, monobridged 2ν6; and state 136, disilavinylidene 2ν6. The computed energies of these states relative to the dibridged ground state are 2006.3, 3488.9, and 4692.0 cm−1, respectively – see Table III for mode numbering.
States with probability densities delocalised along the reaction paths dibridged-monobridged [left and centre] and disilavinylidene-monobridged [right] (totally symmetric states 169, 185, and 218, respectively with computed energies relative to the dibridged ground state of 4900.3, 5012.2, and 5218.7 cm−1).
Nearest neighbour distribution of Si2H2 totally symmetric vibrational energy levels.
States with a high degree of localisation in the trans-bent configuration: trans ground state [left]; trans 2ν6 [centre]; and with delocalisation along the trans-monobridged reaction path [right]. These are totally symmetric states 401, 633, and 944 with computed energies of 5900.8, 6454.4, and 6969.9 cm−1, respectively.
Energies (in cm−1) of the Si2H2 critical points a relative to the dibridged global minimum.
Vibrational mode numbering for Si2H2 isomers. a
Calculated vibrational energies and assignments of Si2H2.
Observed and calculated Si2H2 dibridged fundamentals and inversion splittings for the ground state, fundamentals, and first and second overtones of the ν2 inversion mode.
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