# influence of rotation on the spectra of polyatomic molecules

For simplification think of these two categories as either frisbees for oblate tops or footballs for prolate tops. Introduction. Have questions or comments? If the unique rotational axis has a lower inertia than the degenerate axes the molecule is called a prolate symmetrical top. Generally, polyatomic molecules have complex rotational spectra. In this case, the total rotational energy Equation $$\ref{genKE}$$ can be expressed in terms of the total angular momentum operator $$J^2$$, As a result, the eigenfunctions of $$H_{rot}$$ are those of $$J^2$$ (and $$J_a$$ as well as $$J_Z$$ both of which commute with $$J_2$$ and with one another; $$J_Z$$ is the component of $$J$$ along the lab-fixed Z-axis and commutes with $$J_a$$ because, act on different angles. Legal. Measured in the body frame the inertia matrix (Equation $$\ref{inertiamatrix}$$) is a constant real symmetric matrix, which can be decomposed into a diagonal matrix, given by, $I =\left(\begin{array}{ccc}I_{a}&0&0\\0&I_{b}&0\\0&0&I_{c}\end{array}\right)$, $H_{rot} = \dfrac{J_a^2}{2I_a} + \dfrac{J_b^2}{2I_b} + \dfrac{J_c^2}{2I_c} \label{genKE}$. Only the molecules that have permenant electric dipole moment can absorb or emit the electromagnetic radiation in such transitions. The components of the quantum mechanical angular momentum operators along the three principal axes are: \begin{align} J_a &= -i\hbar \cos χ \left[\cot θ \dfrac{∂}{∂χ} - (\sin θ )^{-1} \dfrac{∂}{∂φ} \right] - -i\hbar \sin χ \dfrac{∂}{∂θ} \\[4pt] J_b &= i\hbar \sin χ \left[\cot θ \dfrac{∂}{∂χ} - (\sin θ )^{-1} \dfrac{∂}{∂φ} \right] - -i\hbar \cos χ \dfrac{∂}{∂θ} \\[4pt] J_c &= - \dfrac{ih ∂}{∂χ} \end{align}, The angles $$θ$$, $$φ$$, and $$χ$$ are the Euler angles needed to specify the orientation of the rigid molecule relative to a laboratory-fixed coordinate system. Since most of the larger polyatomic molecules possess internal rotors with low-lying torsional energy levels, their vapour phase spectra should exhibit influence of torsion on the vibrationalrotational levels. The eigenfunctions $$|J, M,K>$$ are the same rotation matrix functions as arise for the spherical-top case. Consequently, organic compounds will absorb infrared radiation that corresponds in energy to these vibrations. Two simple parallel bands were observed at 8870A and 11590A. Each energy level is therefore $$(2J + 1)^2$$ degenarate because there are $$2J + 1$$ possible K values and $$2J + 1$$ possible M values for each J. In addition to rotation of groups about single bonds, molecules experience a wide variety of vibrational motions, characteristic of their component atoms. Vibrational-Rotational Spectroscopy Vibrational-Rotational Spectrum of Heteronuclear Diatomic Absorption of mid-infrared light (~300-4000 cm-1): • Molecules can change vibrational and rotational states • Typically at room temperature, only ground vibrational state populated but several rotational levels may be populated. Unless otherwise noted, LibreTexts content is licensed by CC BY-NC-SA 3.0. To form the only non-zero matrix elements of $$H_{rot}$$ within the $$|J, M, K\rangle$$ basis, one can use the following properties of the rotation-matrix functions: $\langle j, \rangle = \langle j, \rangle = 1/2 \) are given in terms of the set of rotation matrices $$D_{J,M,K}$$ : \[|J,M,K \rangle = \sqrt{ \dfrac{2J + 1}{8 π^2}} D^* _{J,M,K} ( θ , φ , χ )$, $J^2 |J,M,K \rangle = \hbar^2 J(J+1) | J,M,K \rangle$, $J_a |J,M,K \rangle = \hbar K | J,M,K \rangle$, $J_Z |J,M,K \rangle = \hbar M | J,M,K \rangle$. Missed the LibreFest? in the molecules, the molecule gives a rotational spectrum only If it has a permanent dipole moment: A‾ B+ B+ A‾ Rotating molecule H-Cl, and C=O give rotational spectrum (microwave active). Measured in the body frame the inertia matrix (Equation $$\ref{inertiamatrix}$$) is a constant real symmetric matrix, which can be decomposed into a diagonal matrix, given by, $I =\left(\begin{array}{ccc}I_{a}&0&0\\0&I_{b}&0\\0&0&I_{c}\end{array}\right)$, $H_{rot} = \dfrac{J_a^2}{2I_a} + \dfrac{J_b^2}{2I_b} + \dfrac{J_c^2}{2I_c} \label{genKE}$. the Duschinsky mixing) on the molecular electronic spectra in polyatomic molecules is treated by means of … again for K and M (i.e., $$J_a$$ or $$J_c$$ and $$J_Z$$ quantum numbers, respectively) ranging from $$-J$$ to $$J$$ in unit steps. The angles $$θ$$ and $$φ$$ describe the orientation of the diatomic molecule's axis relative to a laboratory-fixed coordinate system, and $$μ$$ is the reduced mass of the diatomic molecule. This moment of inertia replaces $$μR^2$$ in the denominator of Equation $$\ref{Ediatomic}$$: $E_J= \dfrac{\hbar^2J(J+1)}{2I} = B J(J+1) \label{Ediatomic2}$. For K=0, spectrum reduces to that of linear molecules, no Q branch 4. For more information contact us at info@libretexts.org or check out our status page at https://status.libretexts.org. To form the only non-zero matrix elements of $$H_{rot}$$ within the $$|J, M, K\rangle$$ basis, one can use the following properties of the rotation-matrix functions: $\langle j, \rangle = \langle j, \rangle = 1/2 2 be the number of nuclei in a polyatomic molecule with 3N degrees of freedom. 12Jan2018 Chemistry21b – Spectroscopy Lecture# 5 – Rotation of Polyatomic Molecules The rotational spectra of molecules can be classiﬁed according to their “principal moments of inertia”. Absorption in … Unless otherwise noted, LibreTexts content is licensed by CC BY-NC-SA 3.0. Jack Simons (Henry Eyring Scientist and Professor of Chemistry, U. Utah) Telluride Schools on Theoretical Chemistry. If the unique rotational axis has a lower inertia than the degenerate axes the molecule is called a prolate symmetrical top. The LibreTexts libraries are Powered by MindTouch® and are supported by the Department of Education Open Textbook Pilot Project, the UC Davis Office of the Provost, the UC Davis Library, the California State University Affordable Learning Solutions Program, and Merlot. The rotational spectra of non-polar molecules cannot be observed by those methods, but can be observed … The rotational eigenfunctions and energy levels of a molecule for which all three principal moments of inertia are distinct (a asymmetric top) can not easily be expressed in terms of the angular momentum eigenstates and the $$J$$, $$M$$, and $$K$$ quantum numbers. If the unique rotational axis has a greater inertia than the degenerate axes the molecule is called an oblate symmetrical top (Figure $$\PageIndex{1}$$). H-H and Cl-Cl don't give rotational spectrum (microwave inactive). 13.8: Rotational Spectra of Polyatomic Molecules, [ "article:topic", "moment of inertia tensor", "Rotational of Polyatomic Molecules", "Spherical Tops", "Asymmetric Tops", "Symmetric Tops", "prolate top", "oblate top", "showtoc:no" ], These labels are assigned so that $$I_c$$ is the, The rotational kinetic energy operator for a rigid non-linear polyatomic molecule is then expressed as, The assignment of semi-axes on a spheroid. The eigenfunctions $$|J, M,K>$$ are the same rotation matrix functions as arise for the spherical-top case. \[I =\begin{bmatrix}I_{xx}&I_{xy}&I_{xz}\\I_{yx}&I_{yy}&I_{yz}\\I_{zx}&I_{zy}&I_{zz}\end{bmatrix} \label{inertiamatrix}$, The components of this tensor can be assembled into a matrix given by, $I_{xx}=\sum _{k=1}^{N}m_{k﻿}(y_{k}^{2}+z_{k}^{2})$, $I_{yy}=\sum _{k=1}^{N}m_{k}(x_{k}^{2}+z_{k}^{2})$, $I_{zz}=\sum _{k=1}^{N}m_{k}(x_{k}^{2}+y_{k}^{2})$, $I_{yx}=I_{xy}=-\sum _{k=1}^{N}m_{k}x_{k}y_{k}$, $I_{zx}=I_{xz}=-\sum _{k=1}^{N}m_{k}x_{k}z_{k}$, $I_{zy}=I_{yz}=-\sum _{k=1}^{N}m_{﻿k}y_{k}z_{k}.$, The rotational motions of polyatomic molecules are characterized by moments of inertia that are defined in a molecule based coordinates with axes that are labeled $$a$$, $$b$$, and $$c$$. Legal. However, given the three principal moments of inertia $$I_a$$, $$I_b$$, and $$I_c$$, a matrix representation of each of the three contributions to the general rotational Hamiltonian in Equation $$\ref{genKE}$$ can be formed within a basis set of the $$\{|J, M, K \rangle\}$$ rotation matrix functions. The influence of rotation on spectra of polyatomic molecules. Again, the rotational kinetic energy, which is the full rotational Hamiltonian, can be written in terms of the total rotational angular momentum operator $$J^2$$ and the component of angular momentum along the axis with the unique principal moment of inertia. We also acknowledge previous National Science Foundation support under grant numbers 1246120, 1525057, and 1413739. The resultant rotational energies are given as: $E_J= \dfrac{\hbar^2J(J+1)}{2μR^2} = B J(J+1) \label{Ediatomic}$, and are independent of $$M$$. Vibrational bands, vibrational spectra A-axis N H Influence of Vibration-Rotation Interaction on Line Intensities in Vibration-Rotation Bands of Diatomic Molecules The Journal of Chemical Physics 23 , 637 (1955); 10.1063/1.1742069 Algebraic approach to molecular spectra: Two-dimensional problems This matrix will not be diagonal because the $$|J, M, K \rangle$$ functions are not eigenfunctions of the asymmetric top $$H_{rot}$$. General formalism of absorption and emission spectra, and of radiative and nonradiative decay rates are derived using a thermal vibration correlation function formalism for the transition between two adiabatic electronic states in polyatomic molecules. In contrast to diatomic molecules (Equation \ref{Idiatomic}), the rotational motions of polyatomic molecules in three dimensions are characterized by multiple moments of inertia. levels 2. The components of the quantum mechanical angular momentum operators along the three principal axes are: \begin{align} J_a &= -i\hbar \cos χ \left[\cot θ \dfrac{∂}{∂χ} - (\sin θ )^{-1} \dfrac{∂}{∂φ} \right] - -i\hbar \sin χ \dfrac{∂}{∂θ} \\[4pt] J_b &= i\hbar \sin χ \left[\cot θ \dfrac{∂}{∂χ} - (\sin θ )^{-1} \dfrac{∂}{∂φ} \right] - -i\hbar \cos χ \dfrac{∂}{∂θ} \\[4pt] J_c &= - \dfrac{ih ∂}{∂χ} \end{align}, The angles $$θ$$, $$φ$$, and $$χ$$ are the Euler angles needed to specify the orientation of the rigid molecule relative to a laboratory-fixed coordinate system. Symmetrical tops can be divided into two categories based on the relationship between the inertia of the unique axis and the inertia of the two axes with equivalent inertia. For prolate tops, Equation $$\ref{genKE}$$ becomes, $H_{rot} = \dfrac{J^2}{2I} + J_a^2 \left( \dfrac{1}{2I_a} - \dfrac{1}{2I} \right)$, For oblate tops, Equation $$\ref{genKE}$$ becomes, $H_{rot} = \dfrac{J^2}{2I} + J_c^2 \left( \dfrac{1}{2I_c} - \dfrac{1}{2I} \right)$. typically reflected in an $$3 \times 3$$ inertia tensor. In addition, with the same path length the spectrum from 1.2 to 2.4μ was obtained under low resolution with a photoelectric infra‐red spectrometer. Since the energy now depends on K, these levels are only $$2J + 1$$ degenerate due to the $$2J + 1$$ different $$M$$ values that arise for each $$J$$ value. LINEAR MOLECULES 13 Energy levels, 14-—Symmetry properties, 15—Statistical weights and influence of nuclear spin and statistics, 16—Thermal distribu­ tion of rotational levels, 18—Infrared rotation spectrum, 19—• Rotational Raman spectrum, 20 2. Effects of the quenching cross-section dependence on the rotation rate are examined by numerical calculations for several models. $$B$$ is the rotational constant. However, given the three principal moments of inertia $$I_a$$, $$I_b$$, and $$I_c$$, a matrix representation of each of the three contributions to the general rotational Hamiltonian in Equation $$\ref{genKE}$$ can be formed within a basis set of the $$\{|J, M, K \rangle\}$$ rotation matrix functions. Rovibrational spectra of polyatomic molecules. $E(J,K,M) = \dfrac{h^2 J(J+1)}{2I^2} + h^2 K^2 \left( \dfrac{1}{2I_a} - \dfrac{1}{2I} \right)$, $E(J,K,M) = \dfrac{h^2 J(J+1)}{2I 2} + h^2 K^2 \left( \dfrac{1}{2I_c} - \dfrac{1}{2I} \right)$. U. V. Spectra of Diphenylselenides and Benzyl-Phenyl-Selenides The Influence of a Solvent upon the Electronic Spectra of Polyatomic Molecules Spettri nel Vicino U. V. del p-Fenossi-Difenilsolfuro e Corrispondenti Metil-, Cloro-, Nitro-, Amino- ed Acetilamino-Derivati Rotational spectroscopy is concerned with the measurement of the energies of transitions between quantized rotational states of molecules in the gas phase. again for K and M (i.e., $$J_a$$ or $$J_c$$ and $$J_Z$$ quantum numbers, respectively) ranging from $$-J$$ to $$J$$ in unit steps. grating) in the photographic infra‐red with an absorbing path of up to 60 meters, obtained by multiple reflection according to the method of J. U. The vector coefficients express the asymmetric top eigenstates as, $\psi_n ( θ , φ , χ ) = \sum_{J, M, K} C_{n, J,M,K} |J, M, K \rangle$. As discussed previously, the Schrödinger equation for the angular motion of a rigid (i.e., having fixed bond length $$R$$) diatomic molecule is, $\dfrac{\hbar^2}{2 μ} \left[ \dfrac{1}{R^2 \sin θ} \dfrac{∂}{∂θ} \left(\sin θ \dfrac{∂}{∂θ} \right) + \dfrac{1}{R^2 \sin^2 θ} \dfrac{∂^2}{∂φ^2} \right] |ψ \rangle = E | ψ \rangle$, $\dfrac{L^2}{2 μ R^2 } | ψ \rangle = E | ψ\rangle$, The Hamiltonian in this problem contains only the kinetic energy of rotation; no potential energy is present because the molecule is undergoing unhindered "free rotation". It is oblate if, 13.9: Normal Modes in Polyatomic Molecules, Telluride Schools on Theoretical Chemistry, information contact us at info@libretexts.org, status page at https://status.libretexts.org. In the series of articles we have developed a semiclassical self-consistent approach to calculation of the highly excited rotational states in vibration-rotation (VR) spectra of polyatomic molecules. Jack Simons (Henry Eyring Scientist and Professor of Chemistry, U. Utah) Telluride Schools on Theoretical Chemistry. As a result, the eigenfunctions of $$H_{rot}$$ are those of $$J^2$$ and $$J_a$$ or $$J_c$$ (and of $$J_Z$$), and the corresponding energy levels. for all K (i.e., J a quantum numbers) ranging from -J to J in unit steps and for all M (i.e., J Z quantum numbers) ranging from -J to J. Note: 1. • It was clear what this motion was for diatomic (only one!). Analysis by infrared techniques. It is oblate if, 13.9: Normal Modes in Polyatomic Molecules, Telluride Schools on Theoretical Chemistry, information contact us at info@libretexts.org, status page at https://status.libretexts.org. Infrared and Raman Spectra of Polyatomic Molecules. Because the total angular momentum $$J^2$$ still commutes with $$H_{rot}$$, each such eigenstate will contain only one J-value, and hence $$Ψ_n$$ can also be labeled by a $$J$$ quantum number: $\psi _{n,J} ( θ , φ , χ ) = \sum_{M, K} C_{n, J,M,K} |J, M, K \rangle$. Assume that the molecule rotates as a rigid body, that is, the relative nuclear positions are ﬁxed. The eigenfunctions of $$J^2$$, $$J_Z$$ and $$J_a$$, $$|J,M,K>$$ are given in terms of the set of rotation matrices $$D_{J,M,K}$$ : $|J,M,K \rangle = \sqrt{ \dfrac{2J + 1}{8 π^2}} D^* _{J,M,K} ( θ , φ , χ )$, $J^2 |J,M,K \rangle = \hbar^2 J(J+1) | J,M,K \rangle$, $J_a |J,M,K \rangle = \hbar K | J,M,K \rangle$, $J_Z |J,M,K \rangle = \hbar M | J,M,K \rangle$. typically reflected in an $$3 \times 3$$ inertia tensor. Rotation of Polyatomic Molecules In contrast to diatomic molecules (Equation \ref{Idiatomic}), the rotational motions of polyatomic molecules in three dimensions are characterized by multiple moments of inertia. Pure rotation spectra of polyatomic molecules : 24 (S) Energy levels of a rigid rotor : 25: Polyatomic vibrations: normal mode calculations : 26: Polyatomic vibrations II: s-vectors, G-matrix, and Eckart condition : 27: Polyatomic vibrations III: s-vectors and H 2 O : 28: Polyatomic vibrations IV: symmetry : 29: A sprint through group theory : 30 The rotational energy in Equation $$\ref{Ediatomic}$$ can be expressed in terms of the moment of inertia $$I$$, $I =\sum_i m_i R_i^2 \label{Idiatomic}$. Have questions or comments? Pure rotational Raman spectra. 4- Raman spectroscopy. Symmetrical tops can be divided into two categories based on the relationship between the inertia of the unique axis and the inertia of the two axes with equivalent inertia. For prolate tops, Equation $$\ref{genKE}$$ becomes, $H_{rot} = \dfrac{J^2}{2I} + J_a^2 \left( \dfrac{1}{2I_a} - \dfrac{1}{2I} \right)$, For oblate tops, Equation $$\ref{genKE}$$ becomes, $H_{rot} = \dfrac{J^2}{2I} + J_c^2 \left( \dfrac{1}{2I_c} - \dfrac{1}{2I} \right)$. where $$m_i$$ is the mass of the $$i^{th}$$ atom and $$R$$ is its distance from the center of mass of the molecule. Gerhard Herzberg ... Isolating Equatorial and Oxo Based Influences on Uranyl Vibrational Spectroscopy in a Family of Hybrid Materials Featuring Halogen Bonding Interactions with Uranyl Oxo Atoms. The spectrum of fluoroform has been investigated under high resolution (21‐ft. The angles $$θ$$ and $$φ$$ describe the orientation of the diatomic molecule's axis relative to a laboratory-fixed coordinate system, and $$μ$$ is the reduced mass of the diatomic molecule. We can divide these molecules into four classes in order to interpret the spectra. This matrix will not be diagonal because the $$|J, M, K \rangle$$ functions are not eigenfunctions of the asymmetric top $$H_{rot}$$. Therefore for polyatomic molecules the effect of the interaction on the intensity is smaller than for lighter diatomic molecules, and the rigid rotator model would be a better approximation in this case. Structure of the Spectra of Diatomic Molecules Vibration-Rotation Spectra 129 ... Rotations and Vlbratlons of Polyatomic Molecules 203 Transformation From the Laboratory System to the Molecule-fixed SYMMETRIC TOP MOLECULES 22 Splitting in P and R branch due to a difference in (A-B) in upper and lower vib. The first part concentrates on the theoretical aspects of molecular physics, such as the vibration, rotation, electronic states, potential curves, and spectra of molecules. Vibrational Raman spectra. Since the energy now depends on K, these levels are only $$2J + 1$$ degenerate due to the $$2J + 1$$ different $$M$$ values that arise for each $$J$$ value. 2;:::;R~. The diagonalization of this matrix then provides the asymmetric top energies and wavefunctions. The rotational structure of the two bands was analyzed yielding The K structure in the former was clearly resolved. Thus each energy level is labeled by $$J$$ and is $$2J+1$$-fold degenerate (because $$M$$ ranges from $$-J$$ to $$J$$). The energies associated with such eigenfunctions are, $E(J,K,M) = \dfrac{\hbar^2 J(J+1)}{2I^2}$. CHAPTER I: ROTATION AND ROTATION SPECTRA 13 1. • For a polyatomic, we often like to think in terms of the stretching or bending of a bond. Three principal moments of inertia IA , IB , and IC designated. The LibreTexts libraries are Powered by MindTouch® and are supported by the Department of Education Open Textbook Pilot Project, the UC Davis Office of the Provost, the UC Davis Library, the California State University Affordable Learning Solutions Program, and Merlot. The spectra of polar molecules can be measured in absorption or emission by microwave spectroscopy or by far infrared spectroscopy. Download books for free. The absorption spectrum of CD 3 H has been investigated under high resolution in the photographic infrared with absorbing paths of up to 7 m atmos obtained by multiple reflection. Each of the elements of $$J_c^2$$, $$J_a^2$$, and $$J_b^2$$ must, of course, be multiplied, respectively, by $$1/2I_c$$, $$1/2I_a$$, and $$1/2I_b$$ and summed together to form the matrix representation of $$H_{rot}$$. Splitting in Q branch due to difference in B in upper and lower vib. The energies associated with such eigenfunctions are, $E(J,K,M) = \dfrac{\hbar^2 J(J+1)}{2I^2}$. However, the matrix can be formed in this basis and subsequently brought to diagonal form by finding its eigenvectors {C n, J,M,K } and its eigenvalues $$\{E_n\}$$. Theoretical expressions describing the collisional depolarization of the luminescence of polyatomic molecules in the gas phase are obtained taking into account donor molecule rotation in a dynamic excitation-quenching regime. Molecular Spectra and Molecular Structure III - Electronic Spectra and Electronic Structure of Polyatomic Molecules | Gerhard Herzberg | download | Z-Library. The influence of the normal mode rotation (i.e. Classification of polyatomic molecules 3. Each of the elements of $$J_c^2$$, $$J_a^2$$, and $$J_b^2$$ must, of course, be multiplied, respectively, by $$1/2I_c$$, $$1/2I_a$$, and $$1/2I_b$$ and summed together to form the matrix representation of $$H_{rot}$$. Lecture 4: Polyatomic Spectra Ammonia molecule 1. 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