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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33 views

Rotating orbitals and parameters for a many-body calculation

I am confused with some results I am getting. Given a molecule (In particular, I was toying with triangulenes, some benzenoids and things like that, but this is not very important), I perform first a ...
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Comparing geometries and substrates calculated with DFT for different pathways

As DFT calculation is an excellent tool for confirming and understanding experimental results, I got deep into this field as organic chemist. I successfully isolated interesting transition states (TS) ...
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principal quantum number, azimuthual quantum number sommerfeld

I have come across few books mentioning that principal quantum number (n) is proposed Bohr, Azimuthal quantum number (l) is proposed by Sommerfeld. They also mention that quantum numbers are ...
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63 views

What is meant by “non-relativistic”? [migrated]

I am reading a document on cosmology and particle physics (this s the first time I look into something like this). It frequently states the word "non-relativistic" but I do not understand ...
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1answer
46 views

How can 2 molecular orbitals form simultaneously? [duplicate]

I understand (for example in the case of H2) that two s orbitals produce through constructive interference a bonding orbital and that the out of phase combination of two s orbitals leads to ...
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43 views

Question regarding conflicting results of checking the electron-preciseness of isoelectronic species via NBO and EHM calculations

It is well known that the tert-butyl cation's empty 2p orbital on the central carbon is stabilised by hyperconjugation from neighboring C-H bonds. This would mean that the central 2p "lone pair&...
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19 views

How to transform 'Cartesian gradient' taken from the formatted checkpoint file into the input orientation?

I would like to extract the energy gradient at a particular geometry with many digits from the formatted checkpoint file. However, Gaussian prints the gradient components related to the standard ...
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1answer
92 views

Is the lone electron pair of an amide nitrogen part of the π system when building a Hückel matrix?

Is the lone electron pair of the nitrogen atom part of the conjugated π system in the α,β-unsaturated amide pictured below? Is there a general rule for choosing when to include a nitrogen atom in a ...
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1answer
60 views

Why don't carbon nanotubes behave like quantum dots?

If carbon nanotubes (CNTs) have the size required to have an bound electron energy state, why don't CNTs behave like quantum dots, such as having optical tunability, amongst other properties?
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193 views

Why don't the MO energies sum up to Hartree-Fock SCF value?

I would like to calculate Hartree-Fock energy of $\ce{H3^+}$ ion from orbital energies. So I performed the following calculation in Gaussian 16: ...
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43 views

Probability of finding electron in each orbital

This may include some quantum physics. Are there anyways to describe the wave function of Hydrogen's orbital (or that of a Hydrogen-like atom) in terms of the wave function of each orbital? You can ...
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1answer
61 views

Quantum chemistry Python package to solve the Coupled-Perturbed Hartree–Fock equations

Two of the most well-known Python quantum chemistry pakcages, PySCF and Psi4, can solve the Hartree–Fock equations. However, I am interested in finding analytic derivatives of the electron integrals: $...
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Can actinides form diamagnetic coordination complexes?

I am not sure how accurate I can predict the magnetic properties of actinide diamagnetic complexes, due to the fact that they share the F-block electron as Lanthanides, which are already tricky, ...
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1answer
69 views

Why doesn't the graph of radial part of wavefunction of 2p orbital change its sign? [closed]

Below I have given the graphs of radial part of the wave functions of $\mathrm{2s}$ and $\mathrm{2p}$ orbitals respectively. The graph of the $\mathrm{2s}$ orbital makes sense. It has a radial node ...
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2answers
113 views

Significance of the ground state energy in quantum chemistry?

In quantum mechanics, quantum chemistry, and condensed matter physics courses, it seems like finding the ground state energy of a Hamiltonian is incredibly important. I can understand why having the ...
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25 views

First ionization energy and electron gain enthalpy of dihydrogen / stability comparison of dihydrogen ions [duplicate]

Subset of: How can antibonding orbitals be more antibonding than bonding orbitals are bonding? Stability of $\ce{H2^{-}}<\ce{H2^{+}}<\ce{H2}$ Stability of $\ce{N2^{-}}<\ce{N2^{+}}<\ce{N2}...
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Limitations of Quantum Chemistry [closed]

I have a physics background and I am interested in the applications of quantum mechanics in predicting chemical reactions, and I’m wondering where should I start? I am particularly interested in the ...
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1answer
57 views

How are Quantum Dot molecules formed and what properties do they hold apart differently from singular quantum dots? [closed]

I am trying to understand the science and phenomena behind the function and operation of quantum dot molecules, but the only articles I run into talk about the synthesis of them. Could this be ...
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1answer
119 views

What does the wave function of an electron look like? [closed]

In quantum mechanics, in the 'particle in a box' topic, I studied that by solving the Schrödinger equation, we can actually find out what the wave function of the particle in a box looks like. ...
6
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1answer
58 views

Slater Matrix of Methane Molecule

I am going through Hartree-Fock calculations in detail, but the textbooks I am referring all considered homonuclear molecules as examples. So I am trying to come up with my own the Slater determinant ...
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68 views

Why are electrons filled in fourth shell before the third shell is filled?

I am a beginner and am learning about atomic structure and I am getting confusions regarding the aufbau principle. It is said that the electrons will be filled first in lowest available energy level. ...
3
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1answer
55 views

Is the effective nuclear charge only defined for valence electrons?

I've just been taught about the effective nuclear charge and screening effect in school. I'd like to ask and confirm if the effective nuclear charge is only defined for valence electrons. If not then ...
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1answer
192 views

Oscillator Strength and Absorption Intensity in TDDFT

When I run a linear-response time-dependent DFT calculation in my favourite electronic structure program, for each excitation I'm given an oscillator strength, $f_i$, and transition dipole moment $$\...
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81 views

Using symmetry and group theory arguments to explain iron(II) in a tetrahedral crystal field

I am trying to figure out how to explain $1s \rightarrow 3d$ spectroscopic transitions for $\ce{Fe^{2+}}$ in $T_\mathrm{d}$ symmetry. These transitions make up the pre-edge region in K edge X-ray ...
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32 views

High symmetry points and x-coordinates

Is it possible to work out the x-coordinates related to high symmetry points? The software I'm using doesn't provide me with that, so I was wondering if there is a way to manually figure it out, as I ...
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2answers
95 views

Normalization of a free particle in 1 dimension

I am having difficulty normalizing the wavefunction for a free particle in 1 dimension. I have sent an attachment of my working out. My attempt at the normalisation Free electron: $$-\frac{\hbar^2}{2m}...
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126 views

Hund's rule for comparing term symbol energies in excited state

This question was asked in an exam: The lowest energy electronic state for excited state carbon atom is, a. $^1D_2$ b. $^3D_1$ c. $^3D_3$ d. $^3D_2$ Although we have been taught Hund's rule for ...
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2answers
87 views

How is kinetic energy accounted for when describing diatomic bonds with a Morse potential?

The Morse potential can be used to describe the potential energy of the a diatomic bond: This curve suggests that the lowest state $v = 0$ is the most stable, since it has the lowest potential energy....
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1answer
137 views

Basics of wave-mechanical model of atom

Why is it that for the $\mathrm{d}$ subshell we have $\ \ \mathrm{d}_{xy}, \ \ \mathrm{d}_{yz}, \ \ \mathrm{d}_{xz}, \ \ \mathrm{d}_{x^{2}-y^{2}},$ and $\mathrm{d}_{z^{2}}$ orbitals only? Why aren't ...
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147 views

Why can't the energy of an electron exceed 0 eV?

Today we were learning about atomic structure, our teacher introduced the mathematics of the 'Niels Bohr Model of Atom', and calculated the value of total energy $\frac{-13.6z^2}{n^2} \pu{eV}$. He ...
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91 views

Splitting of atomic orbitals due to Stark effect

I am performing graduate level research on ZEKE Photoelectron Spectroscopy and central to this form of spectroscopy is Rydberg states and the Stark effect. The Stark effect is caused by an electric ...
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1answer
61 views

How to carry out basis set fitting and extrapolation

I am playing around with basis set extrapolations, and i would like to perform some simple tests by doing some parameter fitting and checking the errors. The functional form of the fitted curve is ...
3
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1answer
314 views

Schrödinger equation and degeneracy of atomic orbitals

How does the application of the Schrödinger equation to model a system, such as a particle in a box, help us understand the origin of the degeneracy of atomic orbitals?
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53 views

CCSD and CISD size consistency problem

I have performed a Gaussian16 calculation to explore the size-consistency problem for the CISD and CCSD methods. The system I am studying is the water dimer and the results are not what I expected at ...
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54 views

How would one separate a mixture of isotopes (different nuclear spins) at temperatures near 0 Kelvin?

Suppose we have two isotopes of the same element. For example, isotope A could have a nuclear spin I = 0, isotope B could have nuclear spin I = 3/2. Let us say we have a compound where this element is ...
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1answer
117 views

How does the application of Schrödinger equation to model a particle in a box explain the origin of degeneracy of atomic orbitals?

Is the particle in a box concept analogous to an electron in an orbital? If so, can we apply the equation for the allowed energies of a particle in a box $$E = \frac{h^2n^2}{8mL^2}$$ to the allowed ...
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31 views

Why is the energy levels in hydrogen independent of the quantum numbers l and ml?

I've been looking for an answer for this for quite a bit but I'm still quite confused. On the independence from ml, I think that it originates from the symmetry of the molecule. However, the ...
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1answer
107 views

Does anyone know what program was used to make this molecular structure picture? [closed]

I am a quantum chemistry beginer, and this picture color scheme is classic. I wonder how to make such pictures by myself.
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39 views

Maximum number of Spectral Lines “A better quantum model shows that there will be n^2 transitions”?

I was parsing the following post What is the maximum number of emission lines when the excited electron of a H atom in n = 6 drops to ground state? and came across with the reply from @porphyrin. cite ...
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62 views

TD-DFT transition dipole moment vector does not align with experimental data

I have been modelling excited states of some molecules with similar stucture using TD-DFT theory, however, I have encountered an issue that sometimes transition dipole moment does not align with the ...
4
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1answer
152 views

Potential Energy Curve from Hartree-Fock Calculations

I am currently working on some quantum chemical calculations, in particular looking at dissociation energy curves generated from Hartree-Fock, CI, CCSD and MP2 methods for diatomic molecules. Now, I ...
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1answer
60 views

why we can use the equipartition theorem for translational motion of molecules at room temperature and above because quantization is unimportant

From the book Chemical Principles The Quest for Insight, 5th Edition by Peter Atkins, Loretta Jones The equipartition theorem is a result from classical mechanics; so we can use it for translational ...
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41 views

Quantum numbers associated with electron

I wanted to get your opinion on something. I was given the electron 5p^3 and was told to find the quantum numbers associated with it. I got: n=5 l=1 Ml=1 Ms= +1/2 However, my teacher has told me that ...
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2answers
111 views

Is it true that the better the trial function, the better approximation for the energy in variational principle?

While studying the variational principle in McQuarrie's Quantum Chemistry, I came across the following problem: to relate the difference between an approximation $\phi$ and the exact ground-state wave ...
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1answer
40 views

Fluorescence quenching by palladium(II) vs. platinum(II) complexes

Why do we observe much stronger (in most cases complete) fluorescence quenching by $\ce{Pd^2+}$ than $\ce{Pt^2+}?$ I work with complexes of both metals and there is no real 100% explanation I can find ...
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2answers
48 views

Confusion regarding $\delta$ charge compared with electronegativity

I heard on a lecture of an online site that, let us say, we have two orbitals (1 and 2). Now, it will be like a spherical cloud. Now, what they say is that Now, we can notice that for orbital number ...
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3answers
112 views

Why do electrons have to constantly be moving? [closed]

As a pretense, my understanding of chemistry extends only to a high school honors level. As I know it, electrons occupy orbitals in which they could possibly be situated, and constantly move around ...
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42 views

How to determine the number of π-electrons in a conjugated system from UV-Vis data?

Is there a way to determine the number of π-electrons in a conjugated system from UV-Vis data? I am modelling the electrons as particles in an infinite box of length $L$ equal to the length of the ...
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24 views

Confusions regarding oscillator in black body and value of one quantum [closed]

Q 1 By saying oscillator I.e atoms in the wall of black body. Do we mean electron ? Because boundary of any atom is electron right. Q2 My textbook say that quantum is the smallest value of energy that ...
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43 views

Physical interpreation of coulomb and exchange integral

When trying to solve the Schrodinger equation for the electronic hamiltonian: $$H_{el} = \sum_{i=1}^{N} \bigg( - \frac{1}{2}\nabla_i^2 - \sum_A \frac{Z}{r_{i_A}} \bigg) + \sum_{i>j=1}^{N}\frac{1}{...

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