Questions tagged [quantum-chemistry]

Quantum chemistry is a subfield of quantum mechanics. Like its parent field, quantum chemistry focuses on understanding physical phenomena occuring at the atomic scale. Quantum chemistry however is more focused on providing useful descriptions of electronic structure to aid in understanding chemical problems (e.g. reactions, spectra, dynamics, ...).

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Properties that probe electron kinetic energy

This post is inspired by a question regarding the meaning of off-diagonal elements of the KE matrix (in some AO basis). One answer suggests that a diagonalized KE matrix might not be very useful. I ...
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37 views

Why is the iron inter-system crossing non-negligible at high temperatures?

Inter-system crossing (ISC) is a radiationless process involving forbidden transitions between singlet and triplet state. These are more common with heavy atom molecules, so I understand that ISC is ...
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42 views

Which DFT functional is best for predicting macroscopic properties of molecular liquids?

Which DFT functional (KS-DFT, to be more specific) performs best at predicting macroscopic properties (density, surface tension, boiling point, relative permittivity etc.) of molecular liquids (...
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30 views

Applying the constant number of electrons in DFT density optimisation

(Previous related question: Finding mathematically the ground state density in DFT) I am studying the density optimisation procedure (in particular for Orbital-Free DFT) this thesis. The derivative ...
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87 views

What will happen if electron as a wave undergo destructive interference while travelling in its Orbit?

Today I came across a justification of Bohr's angular momentum quantization using the De- Broglie's hypothesis. The justification said that since the electrons are having wave nature also then while ...
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2answers
710 views

What does Brightness/ intensity of spectral lines depend on?

My book states that it depends upon "The number of photons of same frequency or wavelength ABSORBED or EMITTED" From what I understood, if many hydrogen atoms within the discharge tube EMIT the same ...
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65 views

What will be the form of coulomb and exchange operators for electron m in an n-electron molecule?

I know that the Fock operator for electron $m$ in $n$-electron molecule would be: $$\hat{f}\!(m)u_i(m) = \varepsilon_iu_i(m)$$ $$\hat{f}\!(m) \equiv -\frac 1 2 ∇_m^2 - \sum_α\frac{Z_α}{r_{ma}} + \...
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201 views

Hartree Fock for an atom (Beryllium)?

I'm working on solution of Hartree-Fock equation for Beryllium in configuration $1s^2 2s^2$, expanding the orbital with STO-3G basis $$\phi_k=\sum_{p=0}^3 C_{kp}e^{-\alpha_{kp}r^2}$$ I know the values ...
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91 views

GAMESS Gaussian qst2 method alternative

I've heard about the qst2 Gaussian method but I don't have any licence so I use the free GAMESS-US. Nevertheless, I didn't find any Gamess method which allows a TS finding like qst2. Have you heard ...
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80 views

Antiaromaticity can be explained by Hückel method?

Pentalene is one of the most famous antiaromatic molecules. But I obtained its energy of $\pi$ system as $8\alpha+10.46\beta$ by Hückel method (with a bit complicated but straightforward calculation). ...
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1answer
154 views

Angular momentum of an electron in an atom

The Orbital Angular momentum of an electron in an atom is given by $\hbar \sqrt{l(l+1)}$ and the Spin Angular Momentum is $\hbar \sqrt{s(s+1)}$. So what is the resultant Angular momentum of an ...
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81 views

How is occupation number of lowest unoccupied natural orbital defined?

I have run some calculations to analyse the occupation of natural orbitals. Since it is needed to run in triplet state, I get two orbitals with occupation number 1. Now, which orbital occupation ...
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38 views

Relationship between the 2nd theorem of Hohenberg and Kohn and the Variational Principle

In Density Functional Theory, the 2nd theorem of Hohenberg and Kohn states: The electron density of the system that minimises the ground-state energy is the exact electron density of the system. ...
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74 views

STO 3G basis expansion of p orbitals

I am expanding $2p_{x},2p_{y},2p_{z}$ (slater type )orbitals in gaussian STO-3G basis as follows, $$|2p_{x}\rangle=C_{1}x\exp(-\alpha_{1}r^{2})+C_{2}x\exp(-\alpha_{2}r^{2})+C_{3}x\exp(-\alpha_{3}r^{2}...
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38 views

In 1 dimension, the curvature of Ψ = K.E. of wave. Is this the case for 2 dimensions and 3 dimensions also?

In 1 dimension, the curvature of Ψ = K.E. of wave. Is this the case for 2 dimensions and 3 dimensions also? Moreover, is curvature of Ψ = K.E. of wave = 2nd derivative of Ψ?
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44 views

What is the intuition of using “dimer method” for searching transition states?

I learned dimer method for searching transition state in this paper: A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives. However, I still ...
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612 views

Calculation of average bond length from force constant and IR absorption?

I need some help beginning a problem set problem (just want hints, I'd like to figure it out myself). The problem gives me the IR absorption for a diatomic, as well as the force constant for the ...
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36 views

How on the quantum level do the notch filters used in Raman spectroscopy remove only a select wavelength of light?

From what I have gathered regarding the schematics of Raman spectrometers, the notch filter is used to remove a narrow range of light corresponding to that of the laser used to excite the sample. How ...
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979 views

Difference between Covalent and non-Covalent interactions

It is a general concept that non-covalent interactions are a result of electrostatic interaction while covalent interactions arise due to sharing of electron density. This, however, is not true since ...
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164 views

Why must the ground state of hydrogen molecule be gerade?

As we know, the electronic ground state of hydrogen molecule is $\Sigma_g^+$. My question is, how do we know it from the theoretical perspective? The nuclear potential in the hamiltonian of hydrogen ...
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84 views

Should the normal mode of vibration leading to the transition state be removed?

I would like to know whether the normal mode of vibration of the reactant should be deleted when calculating $\Delta ZPE$ and $\delta G_{\text{corr}}(T)$, where $\Delta ZPE$ is the zero-point energy ...
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43 views

how to understand to what subshell is related basis function in the Eigenvectors block (GAMESS output)?

So, each subshell of some atom is described by one or combination of few BF's. But I can't find correlation between representation of subshells in eigenvectors block and, say, basis set or something ...
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88 views

Spatial form of an atom and type of chemical bond

As we know, the first excited states of Hydrogen atoms is $2p$. The wave functions in cartesian basis we can represent as $$ p_x = \frac{1}{\sqrt{2}} \left( Y_{1, +1} + Y_{1, -1}\right) =\...
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45 views

quantum capacitance of supercapacitor electrodes, high or low needed?

quantum capacitance of supercapacitor electrodes should be low or high? to achieve high specific capacitance. The quantum capacitance forms among the layers of low DOS materials when used as an ...
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108 views

How fast do electron's quantum spin flip?

In a recent lecture it was taught that carbenes with their electrons in a triplet configuration do not undergo concerted reactions as one of the electrons must first undergo a spin flip; on what ...
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56 views

Computational chemistry: is k a quantum number

I am trying to use the natural band offset method to calculate band offsets of junctions. In order to do so, I need to find the core electron eigenstates. I tried using FP-LAPW software Elk. But in ...
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475 views

How does symmetry of half filled and fully filled orbitals lead to stability

I googled a lot about why symmetry of half filled and fully filled orbitals decreases their energy but every time it is repeated that symmetry leads to stability. So the question is why symmetry leads ...
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331 views

Radial nodes in molecular orbitals

Do radial nodes exist in molecular orbitals? Radial nodes exist in atomic orbitals and the number of radial nodes for an atomic orbital can be determined by the general formula $n-l-1$ where $n$ is ...
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44 views

determine at which v and J the rotational and vibrational energy differences are equal

I was presented with this question and I started working on it but I ran into a problem. We've got $\Delta E_{rot} = 2B_e(J+1) $ and $\Delta E_{vib} = \hbar \omega$ We get to the point that we've ...
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564 views

Gaussian: Warning - assumption of classical behavior for rotation may cause significant error

I am playing around with a prostaglandin molecule (23 heavy atoms) in Gaussian09. My goal is to calculate the vertical ionization potential and electron affinity for the molecule. I already managed to ...
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48 views

phase differences between conical intersections and light-induced conical intersections?

I've read recently about light-induced conical intersections, a phenomenon where conical intersections can be artificially introduced to molecules, and that this can be observed even in diatomic ...
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115 views

Calculating Optical Absorption Spectra using Ab Initio Computations

My main question is, How does one compute the optical absorption spectra of a molecule by using say, Configuration Interaction energy and associated transition dipole moments. I am trying to use an ...
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126 views

How do i make an molecular orbital diagram step by step?

My professor explained me, but i'm still unable to do a correct molecular orbital, for a diatomic molecule
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51 views

Why do ionisations from non-bonding orbitals result in little/no vibrational structure in a photoelectron spectrum?

I understand that ionisations from bonding and antibonding orbitals create vibrational structure from the Franck-Condon principle, resulting in a greater overlap integral between different vibrational ...
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165 views

Conical intersection using GAMESS

I would like to know how to locate conical intersection using a GAMESS calculation. I really appreciate an example alone with this since I am a novice I do not have a clear idea among bunch of ...
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39 views

Identifying the dependence of various time-independent wavefunctions

I'm tasked with finding the variables that each of the following wavefunctions depends on: (1) a free particle in 2 space (2) a free particle in 3 space (3) a hydrogen atom (4) a lithium atom. for ...
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62 views

Excitation Source for visible emitting Quantum dots

I read that the best excitation source for visible emitting quantum dots is UV light of wavelength $\mathrm{360~nm}$ to $\mathrm{380~nm}$. But why should the excitation source have lower frequency ...
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179 views

Use of statistics in this field

I am currently pursuing a statistics course and I an interested in knowing how can statistics help this field in future. (I am interested because I love chemistry very much) Specifically, are there ...
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46 views

Sulfur atomic absorption

Would the atomic absorption from FAA for Sulfur be from 3s2 -> 3p4 or 3p4 -> 4s0? I think according to the electronic partition function, there would be zero electrons in the 4s0 state at the ...
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82 views

Help solve this specific linear schrodinger equation, please

$$\left[-\frac{1}{2}\nabla^2 - \frac{2}{r} + C\right]\phi(r) = E\phi(r)$$ where $C$ is a known function. I am just looking for some help on the strategy to solve explicitly for $\phi(r)$. One thing ...
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321 views

How do I calculate principal quantum numbers of the Lyman series

How do I calculate principal quantum numbers of the Lyman series? I've been given that the lowest line is 121.6nm and the 5th line is 93.8nm The formula of the wavenumber is v=-R(1/n2^2 - 1/n1^2) ...
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364 views

QMOT | Orbital mixing in methyl

The following picture is from E. V. Anslyn Physical Organic Chemistry and shows constructing of MO of methyl using QMOT. MOs $\textbf{E'}$ and $\textbf{D'}$ are formed by mixing $\textbf{D}$ and $\...
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89 views

Experimental Validation of Schrodinger's Electron Cloud theory

I am currently doing a report for school on the electron cloud atomic structure theory. One of the major points on my report is the experiments performed by the scientists (Schrodinger and Heisenberg) ...
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1answer
945 views

Physical Meaning of the Difference between MO and VB Wave Function of H2?

What would be the physical meaning of the difference between the MO wave function and VB wave function of $\ce{H2}$?
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43 views

How is it possible to draw a radial wave function for the 2p orbital?

Below is a picture of the radial component of the wave function distribution for the 1 through 3s orbitals. It makes sense to me that there are points where the wave function is 0, since by definition,...
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40 views

Normal (Regular) or Inverted Terms?

I have a question on the order of the spin-orbit molecular states. I understand how to find the terms that split from a parent molecular state in a diatomic molecule. But my question is on how to find ...
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33 views

Cross-conjugation and aromaticity in pyrene

I have read about non-huckel double bonds and clar's rule, but what made me confuse is that huckel's perception gives me the feeling that central bonds in polycyclic aromatic hydrocarbons (ex: pyrene) ...
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15 views

What is the basic difference between accidental degeneracy and normal degeneracy?

As definition suggests accidental degeneracy is defined by the degeneracy generated by two symmetry protected states. But how is it different from a non accidental degeneracy.
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20 views

Approximate Hamiltonian in variational method (Example of Helium atom)

As one know, the exact Helium Hamiltonian \begin{equation} \hat H = \left( -\frac{\hbar}{2m_e}\Delta_1 - \frac{Ze^2}{r_1} \right) + \left( -\frac{\hbar}{2m_e}\Delta_2 ...
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51 views

How to plot the wave function after a Hartree-Fock calculation?

I have written a code in Mathematica and have obtained the final energy of the hydrogen molecule. I have used Gaussian basis functions for this calculation. Now I need to plot the ground state wave ...