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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Electronic States of the (unstable) tetrahedral CrCl4

I was probing for first order Jahn-Teller instability in the coordination complex CrCl4 (2 electrons in E set). Taking the direct product yields the states A1 + A2 + E, so I took the symmetric and ...
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50 views

How to Scan Aromatic Dihedrals To Obtain Force Field Parameters

I am trying to generate new force field parameters based on quantum mechanical calculation. I used amber manual "parameter development" title for this and I calculated bond-angle-non bond parameters ...
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84 views

Antisymmetrized Product of Strongly Orthogonal Geminal (APSG) method

To get a deeper understanding of electronic structure methods, like Hartree-Fock, MP2, and Coupled Cluster method, there are many small programs (codes) available in Python, C++ or Fortran, for ...
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53 views

How to obtain spectroscopic constants Omega_e, Alpha_e, B_e, D_e and D_0 from centrifugal constants?

I need to compute a spectroscopic constants of $N_2^+$ states and I would like to do it using LEVEL16 software, due to its high interpolation flexibility. But it seems, that LEVEL16 can only compute ...
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78 views

Generating density matrix of a wavefunction from common quantum chemistry software

I am looking for density matrixes for a couple of closed shell and open-shell systems, and I wonder if there is a trivial way to make e.g. Gaussian just generate an output for me. I may be wrong but ...
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358 views

Putting high symmetry points labels to a band structure plot

So far I've got this plot using Quantum Espresso. I want to put gamma, X, L, etc labels to the k-path. Quantum Espresso's ouput states the following: ...
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52 views

Calculate molecular orbitals of high-lying or Rydberg states in GAMESS (US)

I am trying to calculate the high-lying or Rydberg orbitals (i.e. unoccupied orbitals with their energies just below the ionization energy) of a nitrogen molecule. I use GAMESS(US) with the following ...
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49 views

Can LCAO be seen as superposition?

In wave physics, when waves interact, the principle of superposition applies. It states that the displacement of the resultant wave is made up of the sum of the individual displacements of the ...
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148 views

Implementing the projected atomic orbital (PAO) localization in Gaussian

I am currently attempting to learn how to setup the active space for performing CASSCF calculations. The textbook I am using as a reference is: Roos, Björn O. "Multiconfigurational quantum ...
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1k views

Chemistry: What's the difference between “binding energy” and “ionization energy”?

In respect to PhotoElectron Spectroscopy (PES), we are analyzing graphs with "binding energy (MegaJoules)" on the x-axis, and with "relative number of electrons" on the y-axis. I have also seen the x-...
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28 views

How to calculate the magnetic exchange coupling in a charged radical complex?

I have a neutral complex with two magnetic centers. For this case it is easy to calculate the exchange coupling as the broken symmetry state is converged properly. But when I am making the complex ...
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158 views

Slater Determinant in Python package

Is there any library functions which I could use in python to construct slater determinant? Can someone suggest me something to fix this issue ? Is it really possible to determinant with functions as ...
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67 views

Calculating the number of energy states in a particular momentum direction

Given is a 2D scenario of a particle within a container: The circumference shows all the possible 2D spatial directions for a given momentum value of the particle. One of those momentum directions is ...
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149 views

Rotational barrier of biphenyl in ground and excited electronic states

I'm studying how the energy of biphenyl varies with its dihedral angle. I know how to describe the dependence quantitatively, but still, I don't know how to explain why the rotational barrier of ...
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127 views

Which natural orbitals are better for CASSCF calculations for organic diradicals?

I am trying to perform CASSCF calculations for a series of diradicals. As input orbitals I have used two types of natural orbitals. One is unrestricted natural orbitals and the other MP2-based natural ...
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133 views

Creating an IR Spectrum using Gaussian ADMP Calculation

I have a Gaussian 16 trajectory for a small cluster of water molecules carried out with ADMP technique. I was wondering if anyone knows how to compute the IR spectrum from the information in the ...
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34 views

QM modelling of charge separation reactions

I have a general question regarding the modelling of reactions in which neutral reactants form charged species/ions (in solution). How can one get the energetics approximately right on reactions like ...
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199 views

Is Argus lab accurate?

I was trying to calculate the resonance energy of benzene by using Argus Lab. These values are weird and very different from the experimental data. I have two questions regarding them. What is the ...
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179 views

Total irreducible representation of a quantum system - Slater determinant?

I'm beginning to study quantum chemistry and I became pretty confused about the total state of the molecule. When we describe the single orbitals using irreducible representations like in the picture ...
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44 views

Why there are just two Ramachandran angles in protein structure for two peptide bonds?

I really want to understand why there are just two ramachandran angles to understand the structure of the protein and why not three or many ? Can someone suggest some reference and explain this ?
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47 views

Can someone suggest me important references for deriving EOM in MCSCF?

I am currently starting a project dealing with MCSCF method. Can someone please give me references (papers or lecture notes are preferred) which may be considered as the "corner stones" in the history ...
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117 views

How can a potential energy function be used to sketch different levels of the wavefunction?

If the potential energy function is provided, say $V(x) = 5x^{2}$, how am I then able to use this function to visualize, graphically, the wavefunction where $V \neq \infty$?
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270 views

How are the Laguerre polynomials and spherical harmonics related to the electronic quantum numbers?

How are the Laguerre polynomials and spherical harmonics related to the quantum numbers $n, l, m_l$ of an electron in an atom?
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85 views

Does restriction on spin in orbits exist?

For a valence electron in Antimony (Sb) with the electron configuration: $Kr(5s)^2(4d)^{10}(5p)^3$ The 3 valence electrons have the quantum numbers $n=5,l=1,m=1$, resulting in the following ...
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94 views

Inactive versus frozen orbitals in CASSCF

Does it make any difference if I use the frozen keyword instead of the inactive keyword in MOLCAS CASSCF calculations?
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42 views

Nomenclature of This State?

I've read this in a book It says the state having three parallel spin is called triplet state . But as far as I know it is determined by "2S+1", from this it comes out to be 4 . Then how it is "...
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318 views

PAW vs USPP: Pseudopotentials in commercial DFT codes

What is the difference between USPP (ultra-soft pseudopotential) and PAW (projector augmented wave) in commercial DFT codes?
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60 views

CF and MO theories: seeing connections between the two approaches

I wonder if and how when considering MO theory, we are accounting for the electrostatic interaction / repulsion between electrons on the metal and the ligand. It seems like MO assumes pure covalency, ...
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201 views

How to determine the permissible values for which solution of the Schrödinger's wave equation exists?

My textbook( A Textbook of Physical Chemistry, Dr. O.P. Tandon ) says that solution of the Schrödinger's wave equation exists only for certain permissible values which are called eigen values.( ...
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192 views

Why are Bohr's formulae for radius and velocity still in use when Heisenberg's uncertainty principle predicts otherwise?

I learnt about Heisenberg's Uncertainty principle which states that it is not possible to determine the position and momentum of a small particle at the same time. I was told that it is because in ...
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63 views

Fitting of interatomic potentials to a training set

I have read several times in the literature the following: "The fittings were accomplished using a combination of the singular value decomposition method for linear parameters and the Simplex method ...
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117 views

What was wrong with Schroedinger's interpretation of the wavefunction?

I've read in a couple of different places, and was told when first learning about quantum mechanics, that Schroedinger interpreted the wavefunction as being representative of the charge distribution ...
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54 views

Absorption and ionization of rare earth ions

I'm studying silicate photosensitive glasses that contain $\ce{Ce}$ ions, and such glasses have an absorption band at 305 nm due to $\ce{Ce^3+}$. After that, the $\ce{Ce^3+}$ ion becomes $\ce{Ce^4+}$, ...
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64 views

Is there wavefunction interference between alternate reaction pathways?

I'll give a specific example to clarify my question. If we look at the approach of chloromethylenecarbene's electron pair to cis-2-butene in the reaction of creating 1-chloro-2,3-dimethylcyclopropane, ...
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790 views

Physicist notation for spatial orbital

In quantum chemistry, the two-electron integrals often denoted as physicist's and chemist's notations. For spin orbital, the physicist's and chemist's notations are $$ \langle pq | rs \rangle = \int ...
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124 views

Quantum Numbers

Why are the Lanthaide (atomic #'s 57-71) elements in period 6, but in terms of electron configuration, are assigned the principal quantum number of 4? Why are certain subshells assigned quantum ...
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135 views

Why does confinement of quantum dots result in discrete energy levels?

I'm doing a project with lead (II) sulfide quantum dots because they have optical transitions in the near infrared. I understand the simple "particle in a box" approach where confinement strengthens ...
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2k views

Magnetic moment of coordination complexes?

To understand the commonly quoted magnetic values of coordination complexes (central ion) we use $$m_l=\sqrt{n(n+2)} \text{BM where BM}=\frac{e\hbar}{2m_e}\text{JT}^{-1}$$ $n$=number of unpaired ...
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33 views

Comparison between Molecular Orbital Theory and Valence Bond Theory

I have been reading about introductory Molecular Orbital Theory lately. Till now, I have used Valence Bond Theory to evaluate bonding. I have a few questions about it:- In VBT, we used the idea that ...
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37 views

Exchange energy

The half filled and full filled configuration is considered to be most the stable among the other configurations. But d7 or d8 configuration has a greater exchange energy mathematically. So why isn't ...
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26 views

spatial degeneracy in the states of atoms and molecules

I would like to know if the exact ground state of a closed-shell atom or molecule can have a spatial degeneracy. If we ignore relativistics effects, the Hamiltonian of the system $H$ commutes with the ...
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106 views

How do you optimize an organo-metalic compound containing cerium in in Gaussian?

I am trying to perform optimisation of the molecule attached. I need to get partial charges and frequencies. The issue is that it doesn't converge with following input: ...
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23 views

Would the 1st excited state of Li2 be vibrationally excited?

I'm quite torn about an interesting past paper question that's come up during my revision, shown below. On the one hand, you're promoting an electron in a bonding orbital. In general, since this ...
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47 views

Wave function of a harmonic oscillator

In a question it is given that consider $H-X$ chemical bond and find $H-X$ bond distance for which there is zero probability density of finding the proton. It is easy to solve we have just to ...
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33 views

Number of nodes in Hartree-Fock solution

The Hartree-Fock equation for atoms is of the form $\left(\frac{d}{dr^2}+f(r)-\epsilon\right)P(r)=g(r) \tag1$ Usually algorithms to solve this equation assumes that the number of nodes of $P(r)$, ...
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37 views

How to assign initial and final states of iodine transitions in its spectrum?

In an experiment, I gently heated iodine crystals to create vapors and then observed it absorption spectrum with a spectrometer. The temperatures throughout were moderate (maximum $40^\circ\text{C}$). ...
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1answer
172 views

What are the steps of Hartree-Fock Theory?

Outline the steps involved in the Hartree–Fock method for the calculation of molecular electronic structure. I understand the basics of HF, in that it does not account for electron correlation (...
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28 views

UV-Vis absorbtion spectra of a radical cation/anion. Is it different compared to its even counterpart?

I am studying gas-phase Uv-Vis spectra of radical molecules. If one electron is removed/captured from the neutral even electron molecule, what can I expect from the absorption spectra? Will new peaks ...
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37 views

Stabilizing donor-acceptor interaction between orthogonal orbitals in the SN2 transition state?

For the $\mathrm{S_N2}$ reaction between chloroacetone and iodide, my professor has drawn a donor-acceptor interaction between the iodine lone pair attacking the Cl-substituted carbon and the π ...
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17 views

What is mass-independent isotope separation/fractionation?

How can any separation/fractionation of isotopes be mass-independent, if the only difference between two isotopes is mass? The only clue(s) on Wikipedia mention molecular symmetry, 'forbidden' spin-...