Kinetic energy of the molecule as a function of the displacements of the atoms from equilibrium positions. For Cartesian displacement coordinates (
\(x, y, z\)),
\[T = \sum_{\alpha}½m_{\alpha}(\dot x_{\alpha }^{2} + \dot y_{\alpha}^{2} + \dot z_{\alpha}^{2})\] where the sum is over all atoms and
\(\dot{x}_{\alpha}\), etc., are the displacement velocities. For internal coordinates
\[T = ½\boldsymbol{P}^{t}\boldsymbol{GP} = ½\dot{\boldsymbol{R}}^{t}{\boldsymbol{G}}^{-1}\dot {\boldsymbol{R}} = ½\sum_{ij}G_{ij}^{-1}\dot R_{i}\dot R_{j}\] where
\(\dot {\boldsymbol{R}}^{t}\) and
\(\dot {\boldsymbol{R}}\) are the row and column vector, respectively, of the
\(\partial R_{i}/\partial t\),
\(\boldsymbol{P}^{t}\) and
\(\boldsymbol{P}\) are the row and column vector, respectively, of the momenta conjugate to the
\(R_{i}\),
\(\boldsymbol{G}^{-1}\) is the inverse of the
\(\boldsymbol{G}\) matrix and
\(G_{ij}^{-1}\) is the
\(ij^{\rm{th}}\) element of
\(\boldsymbol{G}^{-1}\). The elements of the
\(\boldsymbol{G}\) matrix are defined by
\[G_{ij} = \sum_{\alpha}\frac{1}{m_{\alpha}}B_{i\alpha}B_{j\alpha}\] where
\(B_{i\alpha}\) and
\(B_{j\alpha}\) relate the
\(i^{\rm{th}}\) and
\(j^{\rm{th}}\) internal coordinate to the
\(\alpha^{\rm{th}}\) Cartesian coordinate through the equation
\(\boldsymbol{R} = \boldsymbol{BX}\) in which
\(\boldsymbol{X}\) is the column vector of the Cartesian coordinates.
Source:
PAC, 2021, 93, 647. 'Glossary of methods and terms used in analytical spectroscopy (IUPAC Recommendations 2019)' on page 768 (https://doi.org/10.1515/pac-2019-0203)