Questions tagged [group-theory]

The systematic discussion of molecular symmetry is known as group theory. Group theory is a systematic way of describing the symmetry of molecules using concepts/rules borrowed from mathematics. This tag should be applied to any question which involves the theory or application of point groups, symmetry elements, or character tables.

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Pncn space group diagram

I'm trying to make a diagram of the Pncn space group. Firstly, I know that this space group belongs to the orthorhombic system and derives from the point group (2/m 2/m 2/m). Therefore, although the ...
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Molecular Orbitals (only pi system) of Allyl system using group theory

I have just started reading group theory and their applications in the MO theory. I tried to get the equations of the pi molecular orbitals of allyl system using group theory, but I am stuck at the ...
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MOs of Benzene using group theory

I am trying to analyze the $\sigma$ orbitals of benzene molecule using group theory, doing the same thing that is done to the $\pi$ orbitals. The symmetry group of benzene is the $D_{6h}$; considering ...
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Group theory and the orbitals of benzene

Can I apply group theory to the $\sigma$ orbitals of benzene? I have already seen it be applied to the $\pi$ orbitals, but I can't find an application to the $\sigma$ in literature. In this case, ...
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Vanishing integral rule for two-electron integrals

I understand the vanishing integral rule for a one-electron integral to be: $$\langle i | \hat{O} | j \rangle = 0 \hspace{1cm} \mathrm{if} \hspace{0.2cm} \Gamma_O \neq \Gamma_i \otimes \Gamma_j$$ ...
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224 views

Point group from mono to bulk MoS2

Many articles say even numbers of layers or bulk crystal MoS2 have D6h point group and odd numbers of layers (including monolayer) MoS2 have D3h point group But whenever looking at the figure of ...
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How do I get irreducible representations?

I'm currently trying to do a problem where it asks me to "show that the irreducible representations spanned by the atomic x-, y-, and z- coordinates is independent of the choice of local coordinate ...
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How do I interpret characters that are not 1 or -1 in a point group table?

When the character in a point group table is listed as 1 or -1, I understand how an object/orbital etc. transforms to give either itself or the negative of itself. When the character in a point ...
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Misunderstanding about the spin part of the Jahn Teller effect

In the paper Stability if Polyatomic Molecules in Degenerate Electronic States II - Spin Degeneracy the author wrote: Thus a twofold degeneracy cannot produce instability for a molecule containing ...
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What is a “symmetrical product” of an irreducible representation with itself?

In their classic paper outlining the Jahn–Teller theorem (Proc. R. Soc. Lond. A 1937, 161 (905), 220–235), the authors wrote "where $[\phi^2]$ denotes the representation of the symmetrical product of $...
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C5v E1 SALC production using Full Projection

I have another SALC question. @Andrew and @user5713492 did a phenomenal job clarifying my previous confusion with Methane T2 SALC production, so I attempted to apply this to a new point group, and ...
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Methane T2 SALCs

So I have a question on the form of the $T_2$ SALCs of methane. Below I show the $T_d$ character table and the accompanying reducible representation for the sigma framework (using, in the case of ...
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What happens when a symmetry element is added or removed from a point group? [closed]

What new point group is formed if symmetry element i is added to C3 point group?
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What is the symmetry of the cuboctahedron (FCC metal)?

The background to this is that I've recently given a tutorial wherein we had to go through the determination of point groups for atoms in various lattices (BCC, FCC/CCP and HCP). BCC and HCP, I have ...
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How to get $\Gamma_{vib}$ for hexafluoroethane?

An exercise asks me to find $\Gamma_{vib}$ for that molecule. I know that: $$\Gamma_{cart}=\Gamma_{vib}+\Gamma_{translations}+\Gamma_{rot}$$ Since the molecule I'm considering belongs to the $D_{3d}$ ...
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Are there any descent symmetry tables for character tables of linear structures?

I know about tables containing information about descending in symmetry, i.e. from larger point groups to their sub-groups. We can see such tables in this answer, or in this PDF. My question is - ...
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What are t2g and eg in CFT?

In the Crystal Field Theory, when the splitting of the d-orbital occurs, it gets divided into two parts... The upper part with higher Energy is the $t_{2g}$ and the lower part with lower Energy is ...
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Vibronic coupling: How do I determine the new point group after vibration?

So I was recently discussing the transitions in Egyptian Blue ($\ce{CaCu[Si4O10]}$) with some of my students, who had to prepare this compound. What I like in particular in this case is how, at least ...
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Does “higher symmetry” mean any symmetry group of higher order?

What is the precise definition of a higher symmetry in group theory? I see this term scattered around, such as in Cotton's Chemical Applications of Group Theory: ...In the cyclic groups each of the ...
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Cs Point Group's “Horizontal” Reflection Plane

Why is it that $C_s$ character tables always list a $\sigma_h$ operation despite the definition of $C_s$ not necessitating the reflection plane be horizontal? In fact, how can the reflection plane ...
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Why does benzene have 3 π–π* transitions in the UV range, but ethene, butadiene, and hexatriene each have only 1?

Are the π and π* orbitals of benzene much closer together in energy which allows for multiple transitions? Why is this not the case for hexatriene if they both contain the same number of pi bonds?
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Molecular orbital diagram and irreducible representations for dinitrogen

I'm trying to understand how to draw molecular orbital diagrams, since I'd like to use the molecular orbitals to determine the total state of the molecule (i.e. $A_1$, $B_1$ etc.), so I prefer the ...
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Reducible representations - choice of new basis

I was looking at this tutorial about reductions of representations. At first, the basis consists of four orbitals $(s_N, s_1, s_2, s_3)$ and the representations look like this and we want to reduce ...
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N2 symmetry representation in higher symmetry groups (D3h…)

I'd like to describe the symmetry of the ground state of $N_2$ in the higher symmetry groups like $D_{3h}$ and $D_{\infty h}$. In this answer the topic is covered very good, but only for $D_{2h}$ ...
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Reducible representation of planar molecule N2H2 with bond lengths as a basis

I'm studying about molecular symmetry and its representations. Today I got a little confused about the planar $\ce{N2H2}$ molecule. It looks like this The basis in the example was chosen as $\Delta ...
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Finding the irreducible representation which an orbital transforms under [duplicate]

I have some major confusion on irreducible representations. An example of a problem I have is Based on the character table for the point group of each of the follwing molecules, which irreducible ...
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How can I find the symmetry labels of atomic orbitals in a molecule?

What are the symmetry labels for the p and d orbitals of platinum in $\ce{[PtCl4]^2-}$? I understand how to find the point group of a molecule, but am not sure how to use the character table to find ...
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Understanding Equivalent Wyckoff positions

I'm somewhat confused by the concept of Wyckoff positions in crystal structures. From Quantum Chemistry of Solids by Robert Evarestov, the definition of a Wyckoff position is "all the crystallographic ...
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151 views

Would an (NH3)2+ molecule be trigonal planar like BH3 rather than trigonal pyramidal?

I've been learning about using MO theory to explain why $\ce{BH3}$ and $\ce{NH3}$ have different geometries and by following the line of reasoning used to rationalise the differences in geometry I ...
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How to systematically find the reducible representation of a molecule? (eg: XeF4)

I am attempting to use the reduction formula to find the irreducible representation of $\ce{XeF4}$ to determine its IR stretching vibrations. I know the point group of $\ce{XeF4}$ is $D_{4h}$ and have ...
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118 views

Notation for excited states

I am reading some papers about quantum chemistry and in one I found a notation for excited states of a molecule that I don't understand at all. In the picture below you can see the potential curves ...
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Whats the symmetric, anti-symmetric and non-symmetric part of the direct product of irreducible representations?

I am trying to understand how to see if a vibrational mode is Jahn-Teller active or not. According to the group theoretical description of the Jahn-Teller effect one needs to check if the symmetric ...
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Determining overtones bands of degenerate modes

I have a question of a more mathematical nature on the mathSE (Symmetric Direct Product Distributive?) that received a good answer, but I think an answer more oriented to chemists would be a useful ...
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How to dock aggregated structures comprised of “elementary” protein units like LEGO pieces?

There are proteins with intrinsic symmetries. For example: I was wondering how to use transformations such as: rotations, translation, replications to construct possible structures using 2 types of ...
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Why are there no dihedral mirror planes in the D3h point group?

Consider the molecule $\ce{BH3}$, which belongs to the $D_\mathrm{3h}$ point group. Why are the three mirror planes in this point group labelled as $\sigma_\mathrm v$ instead of $\sigma_\mathrm d$? ...
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D3d point group matrices

I am trying to construct all the matrices for the point group D3d operations. I find that the matrices of E, i, S6, inverse of S6, C3, and inverse of C3 are easy, but I do not know how to construct ...
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Why is the letter J omitted in the spdf… sequence?

Under spherical symmetry, the irreducible representations corresponding to $L = 0, 1, 2, \cdots$ are assigned the letters $\mathrm{S}, \mathrm{P}, \mathrm{D}, \mathrm{F}, \cdots$ after which the ...
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Irreducible representations and system states connection

Let's say I have the molecule $\ce{N2+}$. Its symmetry point group is clearly $D_{\infty\mathrm h}$. But I'm confused by its irreducible representations. I know there are 8 of them, but as I ...
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Why are there only two irreducible representations in the C3 group?

There are three elements in a $C_3$ group and there are three classes in this group cause it is an Abelian group. \begin{array}{c|ccc|cc} \hline C_3 & E & C_3 & C_3^2 & & \...
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How do we calculate a character table from its basis functions

This question is a actually a homework question, I'm given the basis functions of all the irreducible representations of $C_{2v}$ group, then I'm asked to complete the character table of $C_{2v}$ ...
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Identifying the C3, C4, S4, and S6 symmetry operations in the Oh point group

The Oh character table has ten symmetry classes. I am trying to identify them, but my stumbling block is in identifying the order of each class. I will use this diagram as a reference, from Sydney ...
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Is there a possible distortion of XeF6 from Oh point group to reduced symmetry?

Below the molecular orbital diagram for $\ce{XeF6}$ (from What is the molecular structure of xenon hexafluoride?) I am trying to figure out if a distortion from $O_h$ can take place and to which (...
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How do I show that a transition is magnetic dipole allowed with group theory/symmetry?

I am taking an introductory course in symmetry and bonding and have so far learnt about SALCs and various point groups etc... one of my problems asks me to show a $\mathrm{^{2}T_{2g}\rightarrow\ ^{2}...
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How is group theory (and matrices) used in symmetry operations? [closed]

I am a high school IB student. For my 2-year math course, there is an internal assessment called "exploration" which should be max. 12 pages long. The goal of this assignment is for students to ...
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What is it that is “symmetry-adapted” about symmetry-adapted perturbation theory?

I think this is a fairly straightforward question which I should know the answer to, but surprisingly cannot find a discussion of online. Symmetry-adapted perturbation theory (SAPT) is a fairly ...
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How do I determine the molecular vibrations of linear molecules?

I know how to do it for just about every other point group, but the $D_{\infty \mathrm h}$ and $C_{\infty \mathrm v}$ character tables aren't as straightforward. In particular, I'm interested in the ...
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Group theoretical condition for an integral to be zero

In many aspects of chemistry it is of interest to find out whether a given integral $\int \psi \,\mathrm{d}\tau$ vanishes, i.e. becomes zero. Group theory provides us with a handy condition: If $\...
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What is the mathematical basis behind the Jahn-Teller effect?

Both first-order and second-order Jahn-Teller distortions play a very important role in chemistry. It is often said that the Jahn-Teller effect is based on symmetry arguments, and hence nothing can ...
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Why do we need the identity operator, E

In group theory, in order to assign a point group, one must first identify the symmetry elements present in the molecule. To give an example, water has: a rotational axis, labelled C2 since it is a ...
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Using group theory to make molecular orbital diagrams

Because of Orthocresols' meta post I ask this question about application of group theory to molecular orbital theory. In my undergraduate lecturers, we've seen many examples of making qualitative MO ...