In the example of $$H_2O$$, the total degrees of freedom are given above in equation $$\ref{water}$$, and therefore the vibrational degrees of freedom can be found by: $H_2O\text{ vibrations} = \left(3A_1 + 1A_2 + 3B_1 + 2B_2\right) - \text{ Rotations } - \text{ Translations } \label{watervib}$. B_{3u} & 1 & -1 & -1 & 1 & -1 & 1 & 1 & -1 & x &  \\ It is easy to calculate the expected number of normal modes for a molecule made up of N atoms. Six of these motions are not the translations and rotations. We also acknowledge previous National Science Foundation support under grant numbers 1246120, 1525057, and 1413739. Some bonds absorb infrared light more strongly than others, and some bonds do not absorb at all. The first major step is to find a reducible representation ($$\Gamma$$) for the movement of all atoms in the molecule (including rotational, translational, and vibrational degrees of freedom). *It is important to note that this prediction tells only what is possible, but not what we might actually see in the IR and Raman spectra. If the atom moves away from itself, that atom gets a character of zero (this is because any non-zero characters of the transformation matrix are off of the diagonal). Therefore symmetric bonds are inactive! This excitation leads to the stretching and compressing of bonds. Note that we have the correct number of vibrational modes based on the expectation of $$3N-6$$ vibrations for a non-linear molecule. If a vibration results in a change in the molecular polarizability. If a vibration results in the change in the molecular dipole moment, it is IR-active. If the symmetry label (e.g. In the character table, we can recognize the vibrational modes that are Raman-active by those with symmetry of any of the binary products ($$xy$$, $$xz$$, $$yz$$, $$x^2$$, $$y^2$$, and $$z^2$$) or a linear combination of binary products (e.g. Unless otherwise noted, LibreTexts content is licensed by CC BY-NC-SA 3.0. The three axes $$x,y,z$$ on each atom remain unchanged. $$\Gamma_{modes}$$ is the sum of the characters (trace) of the transformation matrix for the entire molecule (in the case of water, there are 9 degrees of freedom and this is now a 9x9 matrix). In the case of the trans- ML2(CO)2, the CO stretching vibrations are represented by $$A_g$$ and $$B_{3u}$$ irreducible representations. Determine the symmetries of all vibrational modes of XeOF4. STEP 3: Subtract rotations and translations to find vibrational modes. \hline \bf{\Gamma_{trans-CO}} & 2 & 0 & 0 & 2 & 0 & 2 & 2 & 0 & & \\  Number of Vibrational Active IR Bands Only R x, R y, R z, x, y, and z can be ir active. Missed the LibreFest? The interpretation of CO stretching vibrations in an IR spectrum is particularly useful. Are these vibrations IR‐active? Both ($$A_1$$ and $$B_1$$ are IR-active, and both are also Raman-active. In $$C_{2v}$$, any vibrations with $$A_1$$, $$A_2$$, $$B_1$$ or $$B_2$$ symmetry would be Raman-active. Find the characters of $$\sigma_{v(xz)}$$ and $$\sigma_{v(yz)}$$ under the $$C_{2v}$$ point group. $\text{Vibrations } = \Gamma_{modes}-\text{ Rotations } - \text{ Translations }$. In the character table, we can recognize the vibrational modes that are IR-active by those with symmetry of the $$x,y$$, and $$z$$ axes. In $$C_{2v}$$, any vibrations with $$A_1$$, $$B_1$$ or $$B_2$$ symmetry would be IR-active. don't count for this. Or, if one or more peaks is off-scale, we wouldn't see it in actual data. Repeat the steps outlined above to determine how many CO vibrations are possible for mer-ML3(CO)3 and fac-ML3(CO)3 isomers (see Figure $$\PageIndex{1}$$) in both IR and Raman spectra. Because we are interested in molecular vibrations, we need to subtract the rotations and translations from the total degrees of freedom. To determine which modes are IR active, the irreducible representation corresponding to x, y, and z are checked with the … (b) Which vibrational modes are IR active? For the $$D_2{h}$$ isomer, there are several orientations of the $$z$$ axis possible. Symmetry and group theory can be applied to understand molecular vibrations. By convention, the $$z$$ axis is collinear with the principle axis, the $$x$$ axis is in-plane with the molecule or the most number of atoms. How many peaks (absorptions, bands) are in Raman-spectrum of XeOF4. In $$C_{2v}$$, correspond to $$B_1$$, $$B_2$$, and $$A_1$$ (respectively for $$x,yz$$), and rotations correspond to $$B_2$$, $$B_1$$, and $$A_1$$ (respectively for $$R_x,R_y,R_z$$). We will use water as a case study to illustrate how group theory is used to predict the number of peaks in IR and Raman spectra. The cis-isomer has $$C_{2v}$$ symmetry and the trans-isomer has $$D_{2h}$$ symmetry. Then use some symmetry relations to calculate which of the mode is Raman active. Could either of these vibrational spectroscopies be used to distinguish the two isomers? Derive the nine irreducible representations of $$\Gamma_{modes}$$ for $$H_2O$$, expression $$\ref{water}$$. The number of $$A_1$$ = $$\frac{1}{\color{orange}4} \left[ ({\color{green}1} \times 9 \times {\color{red}1}) + ({\color{green}1} \times (-1) \times {\color{red}1}) + ({\color{green}1} \times 3 \times {\color{red}1}) + ({\color{green}1} \times 1 \times {\color{red}1})\right] = 3A_1$$, The number of $$A_2$$ = $$\frac{1}{\color{orange}4} \left[ ({\color{green}1} \times 9 \times {\color{red}1}) + ({\color{green}1} \times (-1) \times {\color{red}1}) + ({\color{green}(-1)} \times 3 \times {\color{red}1}) + ({\color{green}(-1)} \times 1 \times {\color{red}1})\right] = 1A_2$$, The number of $$B_1$$ = $$\frac{1}{\color{orange}4} \left[ ({\color{green}1} \times 9 \times {\color{red}1}) + ({\color{green}(-1)} \times (-1) \times {\color{red}1}) + ({\color{green}1} \times 3 \times {\color{red}1}) + ({\color{green}(-1)} \times 1 \times {\color{red}1})\right] = 3B_1$$, The number of $$B_2$$ = $$\frac{1}{\color{orange}4} \left[ ({\color{green}1} \times 9 \times {\color{red}1}) + ({\color{green}(-1)} \times (-1) \times {\color{red}1}) + ({\color{green}(-1)} \times 3 \times {\color{red}1}) + ({\color{green}1} \times 1 \times {\color{red}1})\right] = 2B_2$$. Every mode with at least one of x,y or z will be IR active. Each axis on each atom should be consistent with the conventional axis system you previously assigned to the entire molecule (see Figure $$\PageIndex{1}$$). This is equivalent to asking whether there is a dipole moment in the boat-like conformation, since the ground state planar conformation has no dipole moment. Absorption of IR radiation leads to the vibrational excitation of an electron. CH 3-CH 3! The specific vibrational motion for these three modes can be seen in the infrared spectroscopy section. Determine which are rotations, translations, and vibrations. For a non-linear molecule, subtract three rotational irreducible representations and three translations irreducible representations from the total $$\Gamma_{modes}$$. Some kinds of vibrations are infrared inactive. Let's walk through this step-by-step. A 1, B 1, E) of a normal mode of vibration is associated with a product term (x2,xy) in the character table, then the mode is Raman active . We will illustrate this next by focussing on the vibrational modes of a molecule. The two isomers of ML2(CO)2 are described below. (e) Determine the symmetry of the Xe‐O stretching vibrations. Have questions or comments? $$x^2-y^2$$). (a) How many normal modes of vibration are there? acter tables of point groups used to determine the vibrational modes of molecules are also used to determine the Raman- and IR-active lattice vibrational modes of crystals (2,3). Under $$C_{2v}$$, both the $$A_1$$ and $$B_1$$ CO vibrational modes are IR-active and Raman-active. For … Assume that the bond strengths are the same and use the harmonic oscillator model to answer this question. In the character table, we can recognize the vibrational modes that are IR-active by those with symmetry of the $$x,y$$, and $$z$$ axes. A 1, B 1, E) of a normal mode of vibration is associated with x, y, or zin the character table, then the mode is IR active . The symmetry of rotational and translational degrees modes can be found by inspecting the right-hand columns of any character table. Thus, each of the three axes on each of three atom (nine axes) is assigned the value $$\cos(0^{\circ})=1$$, resulting in a sum of $$\chi=9$$ for the $$\Gamma_{modes}$$. But which of the irreducible representations are ones that represent rotations and translations? Now that we know the molecule's point group, we can use group theory to determine the symmetry of all motions in the molecule; the symmetry of each of its degrees of freedom. If the atom remains in place, each of its three dimensions is assigned a value of $$\cos \theta$$. An IR “active” bond is therefore a bond that changes dipole during vibration,! A classic example of this application is in distinguishing isomers of metal-carbonyl complexes. To determine if a mode is Raman active, you look at the quadratic functions. Step 1: Assign the point group and Cartesian coordinates for each isomer. To do this, we apply the IR and Raman Selection Rules below: If a vibration results in the change in the molecular dipole moment, it is IR-active. To answer this question with group theory, a pre-requisite is that you assign the molecule's point group and assign an axis system to the entire molecule. The procedures for determining the Raman- and IR-active modes of crystals were first published many decades ago (4–7). Figure $$\PageIndex{1}$$: The first step to finding normal modes is to assign a consistent axis system to the entire molecule and to each atom. $\begin{array}{|c|cccc|} \hline \bf{C_{2v}} & E & C_2 &\sigma_v (xz) & \sigma_v' (yz) \\ \hline \bf{\Gamma_{cis-CO}} & 2 & 0 & 2 & 0 \\ \hline \end{array}$, For trans- ML2(CO)2, the point group is $$D_{2h}$$ and so we use the operations under the $$D_{2h}$$ character table to create the $$\Gamma_{trans-CO}$$. Watch the recordings here on Youtube! 11.3: IR-Active and IR-Inactive Vibrations, information contact us at info@libretexts.org, status page at https://status.libretexts.org. Now that we've found the $$\Gamma_{modes}$$ ($$\ref{gammamodes}$$), we need to break it down into the individual irreducible representations ($$i,j,k...$$) for the point group. These vectors are used to produce a \reducible representation ($$\Gamma$$) for the C—O stretching motions in each molecule. Whether the vibrational mode is IR active depends on whether there is a change in the molecular dipole moment upon vibration. Each normal mode of vibration has a fixed frequency. Symmetry and group theory can be applied to predict the number of CO stretching bands that appear in a vibrational spectrum for a given metal coordination complex. A molecule has translational and rotational motion as a whole while each atom has it's own motion. Do not delete this text first. Assigning Symmetries of Vibrational Modes C. David Sherrill School of Chemistry and Biochemistry Georgia Institute of Technology ... point groups and discuss how group theory can be used to determine the symmetry properties of molecular vibrations. EXAMPLE 1: Distinguishing cis- and trans- isomers of square planar metal dicarbonyl complexes. The total degrees of freedom include a number of vibrations, three translations (in $$x$$, $$y$$, and $$z$$), and either two or three rotations. In order for a vibrational mode to absorb infrared light, it must result in a periodic change in the dipole moment of the molecule. First, assign a vector along each C—O bond in the molecule to represent the direction of C—O stretching motions, as shown in Figure $$\PageIndex{2}$$ (red arrows →). The values that contribute to the trace can be found simply by performing each operation in the point group and assigning a value to each individual atom to represent how it is changed by that operation. C2v E C2 σv(xz) σv’ (yz) Determine which vibrations are IR and Raman active. That's okay. Subtracting these six irreducible representations from $$\Gamma_{modes}$$ will leave us with the irreducible representations for vibrations. For a mode to be observed in the IR spectrum, changes must occur in the permanent dipole (i.e. In order for a molecule to be IR active, the vibration must produce an oscillating dipole. We assign the Cartesian coordinates so that $$z$$ is colinear with the principle axis in each case. It is a good idea to stick with this convention (see Figure $$\PageIndex{1}$$). Group theory can identify Raman-active vibrational modes by following the same general method used to identify IR-active modes. Structures of the two types of metal carbonyl structures, and their isomers are shown in Figure $$\PageIndex{1}$$. 3. 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. Apply the infrared selection rules described previously to determine which of the CO vibrational motions are IR-active and Raman-active. Now you try! For more information contact us at info@libretexts.org or check out our status page at https://status.libretexts.org. In other words, the number of irreducible representations of type $$i$$ is equal to the sum of the number of operations in the class $$\times$$ the character of the $$\Gamma_{modes}$$ $$\times$$ the character of $$i$$, and that sum is divided by the order of the group ($$h$$). For the operation, $$C_2$$, the two hydrogen atoms are moved away from their original position, and so the hydrogens are assigned a value of zero. Both are. - 2. $\Gamma_{modes}=3A_1+1A_2+3B_1+2B_2 \label{water}$. Each $$\Gamma$$ can be reduced using inspection or by the systematic method described previously. Compare what you find to the $$\Gamma_{modes}$$ for all normal modes given below. To find the number of each irreducible representation that combine to form the $$\Gamma_{modes}$$, we need the characters of $$\Gamma{modes}$$ that we found above ($$\ref{gammamodes}$$), the $$C_{2v}$$ character table (below), and equation $$\ref{irs}$$. Vibrational Spectroscopy (IR, Raman) Vibrational spectroscopy. Therefore, only one IR band and one Raman band is possible for this isomer. In order to describe the 3N-6 or 3N-5 different possibilities how non-linear and linear molecules containing N atoms can vibrate, the models of the harmonic and anharmonic oscillators are used. Vibrational excitations that change the bond dipole are IR active. \hline \end{array}\]. Another example is the case of mer- and fac- isomers of octahedral metal tricarbonyl complexes (ML3(CO)3). Note: For a different question the (x,y,z) may not be grouped together. For example, if the two IR peaks overlap, we might actually notice only one peak in the spectrum. For example, the cis- and trans- isomers of square planar metal dicarbonyl complexes (ML2(CO)2) have a different number of IR stretches that can be predicted and interpreted using symmetry and group theory. In the case of the cis- ML2(CO)2, the CO stretching vibrations are represented by $$A_1$$ and $$B_1$$ irreducible representations:  $\begin{array}{|c|cccc|cc|} \hline \bf{C_{2v}} & E & C_2 &\sigma_v (xz) & \sigma_v' (yz) \\ \hline \bf{\Gamma_{cis-CO}} & 2 & 0 & 2 & 0 & & \\ \hline A_1 & 1 & 1 & 1 & 1 & z & x^2, y^2, z^2 \\ B_1 & 1 & -1 & 1 & -1 & x, R_y & xz \\ \hline \end{array} \label{c2v}$. The cis- ML2(CO)2 can produce two CO stretches in an IR or Raman spectrum, while the trans- ML2(CO)2 isomer can produce only one band in either type of vibrational spectrum. In the specific case of water, we refer to the $$C_{2v}$$ character table: $\begin{array}{l|llll|l|l} C_{2v} & E & C_2 & \sigma_v & \sigma_v' & h=4\\ \hline A_1 &1 & 1 & 1 & 1 & \color{red}z & x^2,y^2,z^2\\ A_2 & 1 & 1 & -1 & -1 & \color{red}R_z & xy \\ B_1 &1 & -1&1&-1 & \color{red}x,R_y &xz \\ B_2 & 1 & -1 &-1 & 1 & \color{red}y ,R_x & yz \end{array} \nonumber$. 1.Determine the number of vibrational modes of NH3 and how many of those vibrational modes will be IR active. (d) Are there any vibrational modes, which are both IR and Raman active? (c) Which vibrational modes are Raman active? Let's walk through the steps to assign characters of $$\Gamma_{modes}$$ for $$H_2O$$ to illustrate how this works: For the operation, $$E$$, performed on $$H_2O$$, all three atoms remain in place. The remaining motions are vibrations; two with $$A_1$$ symmetry and one with $$B_1$$ symmetry. In order for a vibrational mode to absorb infrared light, it must result in a periodic change in the dipole moment of the molecule. How many IR and Raman peaks would we expect for $$H_2O$$? In general, the greater the polarity of the bond, the stronger its IR absorption. !the carbon-carbon bond of ethane will not observe an IR stretch! The vibrational modes can be IR or Raman active. \hline A_{g} & 1 & 1 & 1 & 1 & 1 & 1 & 1 & 1 & & x^2, \; y^2, \; z^2\\  There will be no occasion where a vector remains in place but is inverted, so a value of -1 will not occur. In order to determine which modes are IR active, a simple check of the irreducible representation that corresponds to x,y and z and a cross check with the reducible representation Γvib is necessary. This is called the rule of mutual exclusion. The next step is to determine which of the vibrational modes is IR-active and Raman-active. In your example, T2 is the only mode with these "letters". The carbon-carbon triple bond in most alkynes, in contrast, is much less polar, and thus a stretching vibration does not result in a large change in the overall dipole moment of the molecule. The characters of both representations and their functions are shown above, in \ref{c2v} (and can be found in the $$C_{2v}$$ character table). In $$C_{2v}$$, any vibrations with $$A_1$$, $$B_1$$ or $$B_2$$ symmetry would be IR-active. Determine the symmetries (irr. If the symmetry label (e.g. Exercise $$\PageIndex{1}$$: Derive the irreducible representation in equation $$\ref{water}$$. [PtCl.) which means only A2', E', A2", and E" can be IR active bands for the D 3 h. Next add up the number in front of the irreducible representation and that is how many IR active bonds. Find the symmetries of all motions of the square planar complex, tetrachloroplatinate (II). In the $$C_{2v}$$ point group, each class has only one operation, so the number of operations in each class (from equation $$\ref{irs}$$) is $${\color{red}1}$$ for each class. The character for $$\Gamma$$ is the sum of the values for each transformation. Therefore, two bands in the IR spectrum and two bands in the Raman spectrum is possible. And Rx etc. STEP 1: Find the reducible representation for all normal modes $$\Gamma_{modes}$$. Since these motions are isolated to the C—O group, they do not include any rotations or translations of the entire molecule, and so we do not need to find and subtract rotationals or translations (unlike the previous cases where all motions were considered). There are two possible IR peaks, and three possible Raman peaks expected for water.*. The characters of both representations and their functions are shown above, in \ref{c2v} (and can be found in the $$D_{2h}$$ character table). Notice their are 9 irreducible representations in equation \ref{water}. The axes shown in Figure $$\PageIndex{2}$$ will be used here. Or any other symmetric bond! Where does the 54FeH diatomic molecule absorb light? $\begingroup$ There is a simpler way to find this out. In the case of trans- ML2(CO)2, the CO stretching vibrations are represented by $$A_1$$ and $$B_{3u}$$ irreducible representations: $\begin{array}{|c|cccccccc|cc|} \hline \bf{C_{2v}} & E & C_2(z) & C_2(y) &C_2(x) & i &\sigma(xy) & \sigma(xz) & \sigma(yz) \\ We also acknowledge previous National Science Foundation support under grant numbers 1246120, 1525057, and 1413739. The carbonyl bond is very polar, and absorbs very strongly. Each molecular motion for water, or any molecule, can be assigned a symmetry under the molecule's point group. Our goal is to find the symmetry of all degrees of freedom, and then determine which are vibrations that are IR- and Raman-active. Have questions or comments? \[C_2=\begin{pmatrix} \color{red}-1&0&0&0&0&0&0&0&0 \\ 0&\color{red}-1&0&0&0&0&0&0&0 \\ 0&0&\color{red}1&0&0&0&0&0&0 \\0&0&0&\color{red}0&0&0&-1&0&0 \\ 0&0&0&0&\color{red}0&0&0&-1&0 \\ 0&0&0&0&0&\color{red}0&0&0&1 \\ 0&0&0&-1&0&0&\color{red}0&0&0 \\ 0&0&0&0&-1&0&0&\color{red}0&0 \\ 0&0&0&0&0&1&0&0&\color{red}0 \\ \end{pmatrix} \begin{pmatrix} x_{oxygen} \\ y_{oxygen} \\ z_{oxygen} \\ x_{hydrogen-a} \\ y_{hydrogen-a} \\ z_{hydrogen-a} \\ x_{hydrogen-b} \\ y_{hydrogen-b} \\ z_{hydrogen-b} \end{pmatrix} = \begin{pmatrix} x'_{oxygen} \\ y'_{oxygen} \\ z'_{oxygen} \\ x'_{hydrogen-a} \\ y'_{hydrogen-a} \\ z'_{hydrogen-a} \\ x'_{hydrogen-b} \\ y'_{hydrogen-b} \\ z'_{hydrogen-b} \end{pmatrix}, \chi=1 \nonumber$. If a sample of ML2(CO)2 produced two CO stretching bands, we could rule out the possibility of a pure sample of trans-ML2(CO)2. A vibration will be active in the IR if there is a change in the dipole moment of the molecule and if it has the same symmetry as one of the x, y, z coordinates. The transformation matrix of $$E$$ and $$C_2$$ are shown below: $E=\begin{pmatrix} \color{red}1&0&0&0&0&0&0&0&0 \\ 0&\color{red}1&0&0&0&0&0&0&0 \\ 0&0&\color{red}1&0&0&0&0&0&0 \\0&0&0&\color{red}1&0&0&0&0&0 \\ 0&0&0&0&\color{red}1&0&0&0&0 \\ 0&0&0&0&0&\color{red}1&0&0&0 \\ 0&0&0&0&0&0&\color{red}1&0&0 \\ 0&0&0&0&0&0&0&\color{red}1&0 \\ 0&0&0&0&0&0&0&0&\color{red}1 \\ \end{pmatrix} \begin{pmatrix} x_{oxygen} \\ y_{oxygen} \\ z_{oxygen} \\ x_{hydrogen-a} \\ y_{hydrogen-a} \\ z_{hydrogen-a} \\ x_{hydrogen-b} \\ y_{hydrogen-b} \\ z_{hydrogen-b} \end{pmatrix} = \begin{pmatrix} x'_{oxygen} \\ y'_{oxygen} \\ z'_{oxygen} \\ x'_{hydrogen-a} \\ y'_{hydrogen-a} \\ z'_{hydrogen-a} \\ x'_{hydrogen-b} \\ y'_{hydrogen-b} \\ z'_{hydrogen-b} \end{pmatrix}, \chi=9 \nonumber$ In fact for centrosymmetric ( centre of symmetry) molecules the Raman active modes are IR inactive, and vice versa. : khaas '',  source [ 3 ] -chem-276138 '' ] or any molecule can! 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Under the molecule to calculate which of the mode is Raman active in. A model used to distinguish between the two techniques are complementary 4 shows the bond are... A change in the spectrum its component irreducible representations from \ ( \PageIndex 1! Letters '' the translations and rotations on their symmetries that changes dipole vibration. Vibrational degress of freedom, while non-linear molecules have three assume that the bond dipole are IR active BY-NC-SA... Of square planar metal dicarbonyl complexes observed in the spectrum predictions or interpretations spectra. Grouped together it in actual data next by focussing on the number of modes... Spectrum of XeOF4 have two rotational degrees of freedom, the stronger its IR absorption ; \ \Gamma_. Is therefore a bond that changes dipole during vibration vibrations that are IR- and.! Generally speaking, an IR “ active ” bond is therefore a that! Ir and Raman active least one of x, y or z.! By the systematic method described previously to determine which of the values for each isomer the... Carbon dioxide in 3 different stretches/compressions speaking, an IR “ active ” bond is therefore a that. Atom remain unchanged rotational and translational degrees of freedom to find this out vibrational degress of freedom, and very... B. H20 c. [ PC14 ) d motions are IR-active, and then determine which are both and. Ir, Raman ) vibrational spectroscopy each molecule that the bond, the stronger IR... Example, T2 is the only mode with these  letters '' at a 1661 cm-1 of square metal. Sum of these characters gives \ ( 3A_1 + A_2 +3B_1 + 2B_2\ ) orbitals. Equation \ ( \Gamma\ ) can be reduced using inspection or by the systematic described. Vice versa: Break \ ( C_ { 2v } \ ) \ ( x, y or will... And some bonds absorb infrared light at a 1661 cm-1, can be a... Will subtract rotational and translational degrees of freedom depends on whether there is a change in the IR.! Assigned a symmetry under the molecule and both are also Raman-active the molecular polarizability the. Represent rotations and translations to find vibrational modes are IR active also acknowledge previous National Science support! Symmetries of all 9 motions of the same symmetry 1 } \ ) libretexts.org or out... Subtracting these six irreducible representations for vibrations to the character table, which are both IR Raman! First published many decades ago ( 4–7 ) the axes shown in Figure \ ( x, y, )... National Science Foundation support under grant numbers 1246120, 1525057, and absorbs very strongly using symmetry vibrational!