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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Ionization energy and charge localization: π-bonds/systems and ionization energy

My mass spectrometry textbook says the following in a section on ionization energy (IE) and charge localization: Molecules with π-bonds have lower IEs than those without, causing the IE of ethene ...
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1answer
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Why is there a z² label for d orbitals, but no x² and y² labels with corresponding shapes?

I know that the $\mathrm{d}_{z^2}$ orbitals are named as a result from the conversion of the angular component of the hydrogen-like wave function in terms of Cartesian coordinates, but how come we ...
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Spacial Wavefunction Symmetries and Identical particles

I was reading this and it mentions in the 3-electron section, that for a spacial wave function to be symmetric under fermion swapping, it must be a function of even parity. Similarly for anti-symmetry ...
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Does the radius of the atom change when an electron is excited?

The radius of the atom increases when the electron in a hydrogen atom undergoes a transition from the 1s-orbital to a 2p-orbital. How is this possible? Why does exciting an electron to a higher ...
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Old chemical reaction mechanism under quantum chemistry? [closed]

Quite a few old chemical mechanisms are explained via the old atomic models. After the discovery of quantum chemistry, we have a new atomic and molecular theory like MOT. So how do this old mechanism ...
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How to calculate S² value of a broken-symmetry wave function?

$S$ represents spin, signifies the number of unpaired electrons in the system. For example, if the number of unpaired electrons is $1$, then $S=1/2$. $S^2$ is calculated as $S(S+1)$. From what I have ...
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electron configuration [closed]

I think the answer is E, but can someone help me to make sure
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Stability of subshell of chlorine atom [duplicate]

Why is the valence shell electronic configuration of Chlorine atom 3s2 3p5 and not 3s1 3p6, so that it becomes more stable ?
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Why do solutions of electron in a box (and in a ring) predict coefficients for LCAO (linear combination of atomic orbitals) in 1D systems?

The solutions to the 1D particle in a box quantum mechanic system are standing waves (zero at both ends of the box) with 0,1,2... nodes for increasing energy (zero for the ground state). If I look ...
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1answer
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Ab Initio and Molecular Orbitals [closed]

What is the difference between ab initio calculations and molecular orbital theory?
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1answer
42 views

What does the number of orbitals in a subshell represent? [closed]

s subshell has 1 orbital and p subshell has 3 orbitals. Does that mean that there is a high probability that the electron is in the p subshell? As orbital are the space where there is a high ...
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Gauss primitives located on non-atomic positions

I have the .wfn file including Gauss primitives. And I want to move several primitives to other coordinates... but how can I do it? I know there's a way to make a new atom in appropriate place and ...
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Why does the 4s orbital lose electrons before 3d upon ionization, while it is filled first? [duplicate]

According to AUFBAU, the different energy levels are not filled according to their principal quantum number, for instance 4s is filled before 3d in period 4 transition metals. However when atoms are ...
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Explaining hypervalency in the framework of molecular orbital theory

In preparing for teaching duties in an introductory course in inorganic chemistry, I seem to have made a digression into how we understand the hypervalent molecules. Just to re-iterate what this ...
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All possible determinants forms a complete basis [closed]

How do we mathematically prove that the set of all possible excited determinants forms a complete basis for expanding the wavefunction (as in full configuration interaction)?
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24 views

Guide to DFT functionals [duplicate]

Having recently begun studying Quantum and computational chemistry in depth... I am looking for a manual, text, or guide of any form that could explain the basic formulations and potential of the ...
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Doesn’t an electron change its principal quantum number when travelling through p subshell? [duplicate]

I recently saw an animation of how the electron travels in orbitals around the nucleus. My question is when it’s travelling in the 2p orbital doesn’t it change its principal quantum number when it ...
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1answer
68 views

Quantum numbers required to specify the position of an electron

In a test today, there was this question: How many quantum numbers are required to specify the position of an electron? $$(A)\ 1 \quad (B)\ 2 \quad (C)\ 3 \quad (D)\ 4$$ The answer key says ...
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Multiplicity letter codes for large amount of states

Well, let's say we have a large amount of states computed (e.g. over 50), all with the same multiplicity. So, our ground state can be $X^2\Sigma^+_g$ and we can continue with $B^2, C^2$ etc. as ...
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Getting radial Kohn-Sham orbital from the output of an electronic structure code using gaussian basis sets

As we know that in solving the Schrodinger equation (Kohn-Sham equation), we expand the wavefunction in terms of some basis sets and them optimize the energy (the expectation value of Hamiltonian) by ...
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1answer
79 views

Why is the dz2 orbital so different from the rest?

What makes dz2 orbital so special? Although degenerate with other d orbitals, It has no nodal planes, instead it has 2 nodal "cones". Instead of having 4 lobes, it has 2 lobes and 1 ring. Also, ...
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23 views

What is the significance of antinode at r=0 in the plot of radial wave functions of s-orbitals?

Why should there be an antinode at r=0? I can comprehend the presence of node at r=0 for p,d,f orbitals; but I don't understand that of s-orbital. Is there any intuitive approach?
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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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How To Calculate “İntermolecular Energy” as QM and MM? [closed]

In this article: http://ambermd.org/antechamber/gaff.pdf, in Table-7, authors have calculated "intermolecular energy" of a molecule set. I wonder how can I calculate this energy by using gaussian09 ...
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2answers
181 views

How do you calculate the correct charge on F after F2 dissociates?

When you ionize $\ce{F2}$ to $\ce{F2^5+}$, it quickly dissociates. Experiments show that the products of dissociation are $\ce{F^2+}$ and $\ce{F^3+}$. I have tried to model the dissociation of $\ce{...
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1answer
63 views

Reaction of HF in water [closed]

I was wondering, if we put $\ce{HF}$ into a glass of water the acid will be dissolved according to this reaction: $$\ce{HF->F- + H+}$$ Now there is a proton travelling across the water. All $\ce{...
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1answer
280 views

Why is a LCAO necessary within Hartree Fock?

As I understand it, the electronic Schrödinger equation cannot be solved for polyelectronic systems. To circumvent this problem in the Hartree-Fock method, it is assumed that the polyelectronic ...
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Can pi backdonation occur on non-metal centers?

The common example of back-donation is the interaction of a CO molecule with a metal center (d-orbitals) on a surface. Can a similar mechanism occur between CO and a non-metal center, like oxygen on ...
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1answer
35 views

Chemical reaction energy barrier width [closed]

Well chemistry before the discovery of quantum world was saying:"In order for a chemical reaction to happen , reactants must have enough energy to be converted into products."I was wondering now that ...
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55 views

Variational method: Hydrogen atom ground state in STO-3G basis expansion

I computed numerically the ground state energy of hydrogen by variational procedure, firstly expanding the wave function over the s-wave basis set STO-3G $$\psi(r)=\sum_{i=0}^3 C_{i} e^{-\alpha_ir^2}$$...
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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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3answers
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Particle-wave duality for atoms [closed]

Hmm Hello . I was wondering if we could apply the particle-wave duality of a subatomic particle for an entire atom.I know that atom is better described as space but could we apply the de Broglie ...
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2answers
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When does Hartree-Fock fundamentally fail?

The Hartree-Fock approximation (HFA) works by assuming each electron sees the effective electric field from all the other electrons as some self-consistent field. The HFA is known to give pretty ...
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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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1answer
34 views

Meaning of polarization pulse in microwave (rotational) spectroscopy

In the recent rotational spectroscopy literature, "microwave polarization pulse" is often used in conjuction with pulsed Fourier transform microwave spectroscopy (Google Scholar). Sometimes the pulse ...
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1answer
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Why is the graph of fluorescence vs. wavelength continuous?

If the emission of a photon from an excited state to the ground state occurs with a precise energy, then why is it that wavelengths that differ from lambda max have values on a fluorescence vs. ...
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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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2answers
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How fast is the interconversion triplet → singlet in organic molecules?

When computational studies are performed on transition state geometries, the "thermodynamic" (that is, with no kinetic considerations) energy of the analyzed state is obtained. I was wondering: if a (...
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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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How can I save and read the CI vector during CASSCF calculations in Gaussian?

I have searched through the GAUSSIAN 16 manual and have not been able to solve these two related issues: (1) I want to be able to save the CI vector and load it as an initial guess for a different ...
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What is the theoretical justification for state averaging in SA-CASSCF?

According to the molpro manual, section 7.3: In order to compute excited states it is usually best to optimize the energy average for all states under consideration. This avoids root-flipping ...
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1answer
34 views

Interaction of the oscillating magnetic field of electromagnetic radiation with a molecule or atom

Whenever we read rotational, vibrational and electronic spectroscopy, we find details on the interaction of the electric dipole moment of the molecule with the oscillating electric field of ...
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2answers
81 views

What's the most complete basis set for calculating chemical shifts with DFT?

I'm trying to benchmark some NMR chemical shifts. The literature suggests that the pcS-4 basis set will be the most accurate. I was wondering if there were any basis sets that are more complete than ...
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Why does the exchange interaction in Hartree-Fock theory lower the total energy?

In Hartree-Fock theory, the expectation value of the total energy can be written as $$E = \langle\Psi| H |\Psi\rangle = \sum_{a} \langle a| h |a \rangle + \frac{1}{2}\sum_{ab} \big( [aa |bb] - [ab|ba]...
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Factorizing Slater determinant into product of spin-up and spin-down slater determinant

I am reading the book on MONTE CARLO METHODS IN AB INITIO QUANTUM CHEMISTRY by Hammond and Lester. (Chapter 5-Variational Trial Functions, Section 5.3-Hartree Fock and Beyond, Sub-Section 5.3.3 ...
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1answer
58 views

Computational program not using full cpu power [closed]

I started some computations on Gamess. For instance, when I compute the frequencies of an optimized structure, I see in the terminal that the job only uses 40% of the CPU core most of time (...
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35 views

Is it possible to calculate electrostatic interactions using QM methods?

I'm trying to calculate an accurate electrostatic repulsion (and possibly attraction) energy term for various small molecules, using Quantum Mechanics (QM) methods. These may include molecules such as ...
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1answer
34 views

How to give different Basis set to different atoms in molecules using GAMESS-US [closed]

I am new to GAMESS-US, I am trying to do UHF for DyC10H10 while giving different basis set to Dy, C, H to reduce the computational cast. Until I tried with following input using manual. OUTPUT *** ...
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1answer
167 views

What is the difference between a configuration state function and a Slater determinant?

I do not understand the distinction between configuration state functions and Slater determinants. Is not every Slater determinant a CSF ? Please explain the difference and the use/need of ...
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2answers
63 views

Why is nucleus charge squared in Rydbergs formula?

According to coulumbs law, the energy changes linearly with charge. So why is the nucleus charge squared in this formula? Is there a way to derive it? I was suspecting it might be because it pulls ...