category of computational quantum chemistry technique
Ab initio quantum chemistry methods are a class of computational chemistry techniques based on quantum chemistry that aim to solve the electronic Schrödinger equation. Ab initio means "from first principles" or "from … Wikipedia
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Wikipedia
en.wikipedia.org › wiki › Ab_initio_quantum_chemistry_methods
Ab initio quantum chemistry methods - Wikipedia
December 4, 2025 - Ab initio quantum chemistry methods ... initio means "from first principles" or "from the beginning", meaning using only physical constants and the positions and number of electrons in the system as input....
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PubMed Central
pmc.ncbi.nlm.nih.gov › articles › PMC1100737
Ab initio quantum chemistry: Methodology and applications - PMC
Over the past three decades, ab initio quantum chemistry has become an essential tool in the study of atoms and molecules and, increasingly, in modeling complex systems such as those arising in biology and materials science. The underlying core technology is computational solution of the electronic Schrodinger equation; given the positions of a collection of atomic nuclei, and the total number of electrons in the system, calculate the electronic energy, electron density, and other properties by means of a well defined, automated approximation (a “model chemistry”).
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ScienceDirect
sciencedirect.com › topics › physics-and-astronomy › method-ab-initio
Method Ab Initio - an overview | ScienceDirect Topics
Ab initio methods refer to computational approaches in quantum chemistry that derive molecular orbital treatments from first principles without employing empirical parameters, allowing for more complete calculations compared to semi-empirical methods.
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PNAS
pnas.org › doi › 10.1073 › pnas.0408036102
Ab initio quantum chemistry: Methodology and applications | PNAS
May 10, 2005 - Over the past three decades, ab initio quantum chemistry has become an essential tool in the study of atoms and molecules and, increasingly, in modeling complex systems such as those arising in biology and materials science. The underlying core technology is computational solution of the electronic Schrodinger equation; given the positions of a collection of atomic nuclei, and the total number of electrons in the system, calculate the electronic energy, electron density, and other properties by means of a well defined, automated approximation (a “model chemistry”).
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ScienceDirect
sciencedirect.com › topics › chemistry › ab-initio-calculation
Ab Initio Calculation - an overview | ScienceDirect Topics
Ab initio calculations refer to computational methods that are based solely on fundamental physical laws and postulates, without reliance on experimental data. These calculations utilize principles of quantum mechanics to analyze small molecular systems, employing techniques such as Hartree–Fock ...
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Oxford Reference
oxfordreference.com › display › 10.1093 › oi › authority.20110803095344143
Ab-initio calculation - Oxford Reference
A method of calculating atomic and molecular structure directly from the first principles of quantum mechanics, without using quantities derived from experiment (such as ionization energies found by spectroscopy) as parameters.
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Chemistry LibreTexts
chem.libretexts.org › bookshelves › physical & theoretical chemistry › quantum mechanics in chemistry (simons and nichols) › 20: response theory
20.2: Ab Initio, Semi-Empirical, and Empirical Force Field Methods - Chemistry LibreTexts
December 23, 2016 - This means that they attempt to compute electronic state energies and other physical properties, as functions of the positions of the nuclei, from first principles without the use or knowledge of experimental input.
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Fiveable
fiveable.me › all key terms › general chemistry ii › ab initio methods
Ab initio methods Definition for General Chemistry II |...
Ab initio methods are computational techniques used in quantum chemistry to predict molecular properties and behaviors from first principles, without empirical parameters. These methods rely on fundamental physical theories, such as quantum mechanics, and calculate properties based solely on ...
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ScienceDirect
sciencedirect.com › topics › materials-science › ab-initio-method
Ab Initio Method - an overview | ScienceDirect Topics
In the very early days of studying the structure and the properties of organic compounds in general and fluoropolymers in particular, a very popular method for doing so was by using ab initio methods [28]. Ab initio stands for “from first principles,” meaning that these techniques use quantum ...
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ChemEurope
chemeurope.com › en › encyclopedia › Ab_initio_quantum_chemistry_methods.html
Ab_initio_quantum_chemistry_methods
Ab initio quantum chemistry methods Ab initio quantum chemistry methods are computational chemistry methods based on quantum chemistry.[1] The term ab initio
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Solubility of Things
solubilityofthings.com › ab-initio-methods-and-hartree-fock-theory
Ab Initio Methods and Hartree-Fock Theory | Solubility of Things
Ab initio methods represent a fundamental approach in quantum chemistry, relying on the principles of quantum mechanics to predict molecular structures and properties without empirical parameters. The term "ab initio," derived from Latin, means "from the beginning," indicating that these methods ...
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Computabio
computabio.com › ab-initio-quantum-chemistry-methods.html
Ab Initio Quantum Chemistry Methods - CD ComputaBio
Ab initio quantum chemistry methods attempt to solve the electronic Schrödinger equation given the positions of the nuclei and the number of electrons in order to yield useful information such as electron densities, energies and other properties of the system. ... The simplest type of ab initio electronic structure calculation is the Hartree–Fock (HF) scheme, in which the instantaneous Coulombic electron-electron repulsion is not specifically taken into account.
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Quantum Navigator
entangledfuture.com › home › learn › quantum ab initio methods for chemistry
Quantum Ab Initio Methods for Chemistry | Quantum Navigator
April 9, 2026 - The primary objective of quantum ab initio chemistry is to find the ground state energy and the corresponding wavefunction of a molecular system by diagonalizing the molecular Hamiltonian in a suitable basis set.
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Ststephens
moodle.ststephens.net.in › pluginfile.php › 355 › mod_resource › content › 2 › Abinitio methods in chemistry.pdf pdf
Semester 2 M.Sc [Type here] St. Stephens Uzhavoor 1 Ab Initio
The term "Ab Initio” means “from the beginning". This name is given to computations which are · derived directly from theoretical principles, with no inclusion of experimental data. Most of the · time this is referring to an approximate quantum mechanical calculation.
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SciSpace
scispace.com › pdf › an-experimental-chemist-s-guide-to-ab-initio-quantum-2bf3vhgbl8.pdf pdf
J. Phys. Chem. zyxwvut 1991, 95, zyxwvut 1017-1029 1017 FEATURE ARTICLE
of ab initio quantum chemistry are overviewed. In these sections, the Hartree-Fock (HF), configuration interaction (CI), multiconfigurational self-consistent field (MCSCF), Maller-Plesset perturbation theory (MPPT), coupled-cluster (CC), and density functional methods such as X, are introduced. The strengths and weaknesses of these methods as well as the · computational steps involved in their implementation are briefly discussed. 1. What Does ab Initio Quantum Chemistry Try zyxwvuts
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There's three scenarios that come to my mind, for when ab initio methods get abandoned:

  • The cost becomes prohibitive (e.g. too many electrons)
  • The insight is lost
  • It is simply not required for what we want to do

Prohibitive cost: If solving the Schrödinger equation (for example) is no longer possible, we may very well still wish we could solve the Schrödinger equation, but we are unfortunately forced to make simplifications. For example, you can switch to a Hückel model of the Hamiltonian, and the benefits and uses of Hückel theory were discussed in this mini-publication that Etienne Palos wrote for his answer to this question: Where is the extended Hückel method (EHM) still used today?

Insight is lost: A major disadvantage of ab initio methods, is akin to the disadvantage of solving a differential equation, or finding the eigenvalues of a matrix numerically rather than analytically. When you solve a differential equation or find matrix eigenvalues analytically, you can see explicitly the dependence of the answer on each parameter. For example if the lowest eigenvalue of a matrix is $\lambda = \frac{5D^2}{\sqrt{\pi}}$ for some diffusion constant $D$, then not only can you now calculate the answer for various other values of $D$ easily, you can also see right away that $\lambda = \mathcal{O}(D^2)$ which can be a very powerful thing to know. To find the eigenvalue numerically you will need to substitute a number for $D$ and then you'll just get a number such as $\lambda=5.22195$. To discover the $D^2$ dependence, you will have to re-do the calculation for many other values of $D$. But there is an advantage to numerically finding the eigenvalue, and that is that you can do this for arbitrary diagonalizable matrices of size $1000\times 1000$ (for example) extremely quickly (so perhaps re-consider your first statement, that ab initio methods are "slow") whereas it in general would be impossible to solve the problem analytically. The situation is very similar for model Hamiltonians vs ab initio treatments: when you solve for the ground state energy of a 50-electron Schrödinger equation, you just get a number, but if you do this for an exactly solvable Ising or Hubbard Hamiltonian, you might get a formula.

Not required: In this paper in the field of "quantum biology", I modeled quantum mechanically the FMO pigment-protein complex, which contains 24 fairly large molecules called chromophores, embedded within a protein which is dissolved in water. The system contains thousands of particles. Did I solve the Schrödinger equation for thousands of particles? No, because the purpose was to study the rate of energy transfer from the first chromophore to three specific "end" chromophores and it could easily be done in the following way: each of the 24 chromophores can either be in its ground state or electronic excited state, but there is exactly enough energy in the system for only one of the chromophores to be excited at any given point in time, so we can ignore ground states that have zero excitations and we can ignore the second, third, fourth, etc. excited states. We therefore have a single-excitation subspace of 24 possible states (one for each possible chromophore containing the single excitation). Each of these states has an energy relative to the lowest one: these are diagonals of my single-excitation model Hamiltonian. There's a tunelling amplitude between each pair of states: these are the off-diagonals of my single-excitation model Hamiltonian. The vibrations of the protein and water around the chromophores will certainly affect the dynamics of energy transfer, and these involve thousands of atoms, but we roughly know the "spectral distribution functions" $J_m(\omega)$ for each single-excitation state $m$, where $J_m(\omega)$ tells us how strongly state $m$ interacts with vibrations of frequency $\omega$. We then have a $24 \times 24$ matrix describing the electronic degrees of freedom and twenty-four $J(\omega)$ functions describing the effect of nuclear vibrations on these, and we use the numerically exact Feynman-Vernon equation to calculate how the excitation evolves. If we tried to solve the entire problem ab initio we could get much more detailed information about the system's wavefunction, but we really do not need those details in this case, and the difference we would get for the overall result would unlikely provide any further valuable information to the study.

I'd like now to try to address some of the comments in your question:

  • I would try not to get to caught up about "differences" between "physicists" and "chemists" here. It is not true that "physicists" do not do ab initio calculations, for example Krzysztof Pachucki does some of the most high-precision ab initio atomic calculations in the world, and also some molecular ab initio calculations, but more people would call him a "physicist" than a "chemist" (his degrees are also all in physics and he's in a physics department). Likewise Gordon W. F. Drake, who was the "Editor in Chief" of Physical Review A for decades, also got all his degrees in physics, worked in physics departments for his entire career, and was elected an APS Fellow but probably was never even considered for an ACS Fellow designation, does ab initio calculations on atoms, as do a fair number of other atomic physicists.
  • On another front, ab initio methods are getting popular as a more rigorous way to study high-Tc superconductive materials in a first-principles way, see for example:
    • "New superexchange paths due to breathing-enhanced hopping in corner-sharing cuprates" and,
    • "Towards an exact description of electronic wavefunctions in real solids".
  • "There are extra approximations in any ab initio calculation in order to make the many-body Schrödinger equation tractable. For many applications, these approximations (especially the Born-Oppenheimer approximation) are unacceptable." That's not really true. We do non-Born-Oppenheimer ab initio calculations frequently: Are there examples of ab initio predictions on small molecules without the "major approximations"?. There's excellent review papers on the subject by Ludwik Adamowicz, for example:
    • "Non-Born–Oppenheimer calculations of atoms and molecules",
    • "Born–Oppenheimer and Non-Born–Oppenheimer, Atomic and Molecular Calculations with Explicitly Correlated Gaussians".
  • "Ab initio methods do not capture the physics of strongly correlated systems properly for some reason." Who said so? The ab initio method called CASSCF is used to (accurately) treat strong correlation in thousands of studies, and it is such a popular method that it's implemented in several open source software packages: Is there a free package with robust CASSCF functionality?
  • "Maybe there is some deep reason about "quantum protectorates" and how the many-body Schrödinger equation is not sufficient to describe some systems, and a "higher" theory is needed (this seems quite philosophical and hard to prove, though)." If that's the case, what makes you think your model Hamiltonian such as an Ising or Hubbard Hamiltonian, will work? Those model Hamiltonians are just approximations of the Hamiltonian that Schrödinger told us. ab initio methods try to solve the "true" the Schrödinger equation, whereas model Hamiltonians approximate it a bit first, then solve.
  • Just because it's in a book doesn't mean it's true. That quote alone is enough to tell us that the book's author is biased against ab initio methods, and doesn't even quite know what they are. It is not correct that "there are always approximations inherent to them, in particular the reliance on the Born–Oppenheimer approximation" as I already showed above two review papers on non-Born-Oppenheimer ab initio calculations. The author then goes on to say "and often the local density approximation for exchange and correlation" as if the GGA and meta-GGA and other DFT functionals that are not LDA are not approximations? Also, density functionals are almost always fitted to experimental data so a very large number of people don't consider density functional calculations to be ab initio, see: Can DFT be considered an ab initio method? and Is density functional theory an ab initio method?.
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Wiley Online Library
wires.onlinelibrary.wiley.com › doi › 10.1002 › wcms.1706
Making quantum chemistry compressive and expressive: Toward practical ab‐initio simulation - Yang - 2024 - WIREs Computational Molecular Science - Wiley Online Library
March 12, 2024 - This idea conceptually derives from the nature of real physical interactions in molecular Hamiltonians,77 and leads to a number of compressive and selective wavefunction representations implemented in state-of-the-art strong correlation methods for ab-initio quantum chemistry, including the density matrix renormalization group (DMRG),78-83 the selected or adaptive CI,84-92 the many-body expansion full CI,93, 94 the heat-bath CI,95, 96 the downfolded CI,97 the CC reduction,98-101 and selective high-level CC methods,102-104 a variety of stochastic quantum Monte Carlo CI approaches,105-109 and qu
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PubMed
pubmed.ncbi.nlm.nih.gov › 15870212
Ab initio quantum chemistry: methodology and applications - PubMed
May 10, 2005 - 1 Department of Chemistry, Columbia University, 3000 Broadway, MC 3110, New York, NY 10025, USA. rich@chem.columbia.edu ... This Perspective provides an overview of state-of-the-art ab initio quantum chemical methodology and applications. The methods that are discussed include coupled cluster theory, localized second-order Moller-Plesset perturbation theory, multireference perturbation approaches, and density functional theory.