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Physlib.QuantumMechanics.Hydrogen.Rydberg

The Rydberg formula and the spectral series of the hydrogen atom

i. Overview

The bound-state energies expected for the `d`-dimensional hydrogen atom with potential `-k / r` are `E_n = -Ry / (n + (d - 1) / 2) ^ 2` for `n : ℕ`, with the Rydberg energy `Ry = m k ^ 2 / (2 ℏ ^ 2)`. This module defines these Bohr levels and derives from them, by algebra alone, the Rydberg formula for the energy, the frequency and the wavelength of the photon emitted in a transition between two levels, together with the Lyman, Balmer and Paschen series and their series limits.

The statement that these values are the point spectrum of the hydrogen Hamiltonian is not proved here; it is a separate TODO of the `Basic` module. Nothing in this module depends on the Hamiltonian.

ii. Key results

Definitions: - `rydbergEnergy` : the Rydberg energy `Ry = m k ^ 2 / (2 ℏ ^ 2)`. - `levelIndex` : the effective principal quantum number `L n = n + (d - 1) / 2`. - `energyLevel` : the Bohr levels `E_n = -Ry / L n ^ 2`. - `transitionFrequency` : the frequency `ν = (E_{n₂} - E_{n₁}) / h` of the photon emitted in the transition from `n₂` to `n₁`, and `wavelength` its wavelength `c / ν`. - `rydbergFrequency` : the Rydberg frequency `R_ν = Ry / h`. - `lymanFrequency`, `balmerFrequency`, `paschenFrequency` : the three classical series.

Lemmas: - `energyLevel_strictMono` : the Bohr levels increase strictly with `n` when `2 ≤ d` and `k ≠ 0`. - `transitionFrequency_eq` : the Rydberg formula `ν = R_ν (1 / L n₁ ^ 2 - 1 / L n₂ ^ 2)`. - `wavelength_inv` : its wavenumber form `1 / λ = (R_ν / c) (1 / L n₁ ^ 2 - 1 / L n₂ ^ 2)`. - `tendsto_transitionFrequency` : the series limit `ν → R_ν / L n₁ ^ 2` as `n₂ → ∞`. - `balmerFrequency_lt_lymanFrequency` : for `2 ≤ d ≤ 5`, every Balmer line lies below every Lyman line.

iii. Table of contents

  • A. The Bohr levels
  • B. Transitions and the Rydberg formula
  • C. The spectral series

iv. References

* None.

A. The Bohr levels

The Rydberg energy `Ry = m k ^ 2 / (2 ℏ ^ 2)` sets the scale of the spectrum, and the level index `L n = n + (d - 1) / 2` is the effective principal quantum number in dimension `d`; for `d = 3` it is `n + 1`, the usual principal quantum number, with `n = 0` the ground state.

B. Transitions and the Rydberg formula

A transition from the level `n₂` down to the level `n₁` emits a photon of energy `E_{n₂} - E_{n₁}`, frequency `ν = (E_{n₂} - E_{n₁}) / h` and wavelength `λ = c / ν`, with `c` the speed of light. The Rydberg formula expresses these through the Rydberg frequency `R_ν = Ry / h`, the frequency of a photon carrying the Rydberg energy.

The same definitions are used for any pair of levels. When `2 ≤ d` and `k ≠ 0` and `n₂ < n₁`, the level `n₂` lies below `n₁`: the transition from `n₂` to `n₁` goes up and absorbs a photon, and the frequency and the wavelength defined here are then negative, their absolute values being those of the absorbed photon. For `n₁ = n₂` there is no photon and the frequency is `0`.

C. The spectral series

The Lyman, Balmer and Paschen series collect the transitions down to the levels of index `0`, `1` and `2`; for `d = 3` these are the levels `n = 1`, `2` and `3` of the usual numbering.

43 declarations

definition

Rydberg energy RyRy

The Rydberg energy RyRy of a hydrogen-like atom is defined as Ry=mk22ℏ2Ry = \frac{m k^2}{2 \hbar^2} where mm is the mass, kk is the potential constant, and ℏ\hbar is the reduced Planck constant.

theorem

Ry=mk22ℏ2Ry = \frac{m k^2}{2 \hbar^2}

The Rydberg energy RyRy of a hydrogen-like atom is given by the formula Ry=mk22ℏ2Ry = \frac{m k^2}{2 \hbar^2} where mm is the mass, kk is the potential constant, and ℏ\hbar is the reduced Planck constant.

definition

Level index LnL_n of the nn-th Bohr level

For a natural number nn, the level index LnL_n (also known as the effective principal quantum number) of the nn-th Bohr level in a dd-dimensional hydrogen atom is defined as: Ln=n+d−12 L_n = n + \frac{d - 1}{2} In the specific case of d=3d = 3, this corresponds to the standard principal quantum number n+1n + 1.

theorem

Ln=n+(d−1)/2L_n = n + (d - 1) / 2

For a dd-dimensional hydrogen atom, the level index LnL_n (the effective principal quantum number) for a given natural number nn is defined by the formula: Ln=n+d−12 L_n = n + \frac{d - 1}{2} where dd is the dimension of the atom.

definition

nn-th Bohr energy level EnE_n

For a natural number nn, the nn-th Bohr energy level EnE_n of a dd-dimensional hydrogen atom is defined as: En=−RyLn2 E_n = -\frac{Ry}{L_n^2} where RyRy is the Rydberg energy and Ln=n+d−12L_n = n + \frac{d - 1}{2} is the effective principal quantum number (or level index). These values represent the expected bound-state energies of the hydrogen atom Hamiltonian. In the case where d=1d = 1 and n=0n = 0, the level index LnL_n is zero and the energy level EnE_n is defined to be 00.

theorem

Bohr energy level formula En=−Ry/Ln2E_n = -Ry / L_n^2

For a dd-dimensional hydrogen atom and a natural number nn, the energy of the nn-th Bohr level EnE_n is given by: En=−RyLn2 E_n = -\frac{Ry}{L_n^2} where RyRy is the Rydberg energy and LnL_n is the level index (the effective principal quantum number), defined as Ln=n+d−12L_n = n + \frac{d - 1}{2}.

theorem

Ry≥0Ry \ge 0

The Rydberg energy RyRy is non-negative, meaning Ry≥0Ry \ge 0.

theorem

Ry>0Ry > 0 if k≠0k \neq 0

Let kk be the potential constant and RyRy be the Rydberg energy of a hydrogen-like atom. If k≠0k \neq 0, then the Rydberg energy is strictly positive (Ry>0Ry > 0).

theorem

k=0  ⟹  Ry=0k = 0 \implies Ry = 0

If the potential constant k=0k = 0, then the Rydberg energy Ry=0Ry = 0.

theorem

The level index LnL_n is non-negative for d≠0d \neq 0

For a dd-dimensional hydrogen atom where the dimension d≠0d \neq 0, the level index LnL_n (also known as the effective principal quantum number) is non-negative for any n∈Nn \in \mathbb{N}. That is, 0≤Ln0 \leq L_n, where the level index is defined as Ln=n+d−12L_n = n + \frac{d - 1}{2}.

theorem

Ln>0L_n > 0 for d≥2d \geq 2

For a dd-dimensional hydrogen atom, if the dimension satisfies d≥2d \geq 2, then for any natural number n∈Nn \in \mathbb{N}, the level index Ln=n+d−12L_n = n + \frac{d - 1}{2} is strictly positive (Ln>0L_n > 0).

theorem

The level index LnL_n is strictly increasing

For a dd-dimensional hydrogen atom, the level index (effective principal quantum number) defined as Ln=n+d−12L_n = n + \frac{d - 1}{2} is strictly increasing with respect to the natural number nn. That is, for any n1,n2∈Nn_1, n_2 \in \mathbb{N}, if n1<n2n_1 < n_2, then Ln1<Ln2L_{n_1} < L_{n_2}.

theorem

LnL_n is monotone

The level index LnL_n (effective principal quantum number) of a dd-dimensional hydrogen atom, defined as Ln=n+d−12L_n = n + \frac{d - 1}{2} for n∈Nn \in \mathbb{N}, is monotone. That is, for any natural numbers n1n_1 and n2n_2, if n1≤n2n_1 \le n_2, then Ln1≤Ln2L_{n_1} \le L_{n_2}.

theorem

The Bohr energy levels EnE_n are non-positive (En≤0E_n \leq 0)

For any natural number nn, the nn-th Bohr energy level EnE_n of the dd-dimensional hydrogen atom is non-positive, i.e., En≤0E_n \leq 0.

theorem

En<0E_n < 0 for d≥2d \ge 2 and k≠0k \neq 0

For a dd-dimensional hydrogen atom with potential constant kk, if the dimension satisfies d≥2d \geq 2 and the potential constant k≠0k \neq 0, then for any natural number nn, the nn-th Bohr energy level EnE_n is strictly negative, i.e., En<0E_n < 0.

theorem

En=0E_n = 0 when k=0k = 0

Suppose the potential constant kk of a dd-dimensional hydrogen atom is 00. Then for any natural number nn, the nn-th Bohr energy level EnE_n is equal to 00.

theorem

Bohr energy levels EnE_n are strictly increasing for d≥2d \geq 2 and k≠0k \neq 0

In a dd-dimensional hydrogen atom with potential parameter k≠0k \neq 0 and dimension d≥2d \geq 2, the sequence of Bohr energy levels EnE_n is strictly increasing with respect to nn. That is, for any natural numbers n1<n2n_1 < n_2, the corresponding energy levels satisfy En1<En2E_{n_1} < E_{n_2}.

theorem

d≥2  ⟹  d \ge 2 \implies Monotonicity of Bohr energy levels EnE_n

For a dd-dimensional hydrogen atom, if the dimension d≥2d \ge 2, then the sequence of Bohr energy levels EnE_n is monotonically increasing. That is, for any natural numbers nn and mm, if n≤mn \le m, then En≤EmE_n \le E_m.

definition

Transition energy En2−En1E_{n_2} - E_{n_1}

For two natural numbers n1n_1 and n2n_2, the transition energy is the difference between the n2n_2-th and n1n_1-th Bohr energy levels, defined as En2−En1E_{n_2} - E_{n_1}. This represents the energy associated with a transition between these two levels.

theorem

Transition energy equals En2−En1E_{n_2} - E_{n_1}

For any two natural numbers n1n_1 and n2n_2, the transition energy between the corresponding Bohr energy levels is the difference between the n2n_2-th energy level and the n1n_1-th energy level: ΔE(n1,n2)=En2−En1 \Delta E(n_1, n_2) = E_{n_2} - E_{n_1} where EnE_n denotes the nn-th energy level `energyLevel n` and ΔE(n1,n2)\Delta E(n_1, n_2) denotes the transition energy `transitionEnergy n₁ n₂`.

definition

Transition frequency ν=En2−En1h\nu = \frac{E_{n_2} - E_{n_1}}{h}

For two natural numbers n1n_1 and n2n_2 representing energy levels of a hydrogen atom, the transition frequency is defined as the ratio of the transition energy En2−En1E_{n_2} - E_{n_1} to the Planck constant hh: ν=En2−En1h\nu = \frac{E_{n_2} - E_{n_1}}{h} This value is positive when n1<n2n_1 < n_2 (corresponding to the emission of a photon), negative when n2<n1n_2 < n_1 (corresponding to the absorption of a photon with frequency ∣ν∣|\nu|), and zero when n1=n2n_1 = n_2.

theorem

Transition Frequency ν=ΔE/h\nu = \Delta E / h

For any two natural numbers n1n_1 and n2n_2 representing energy levels of a hydrogen atom, the transition frequency ν\nu between these levels is equal to the transition energy ΔE(n1,n2)\Delta E(n_1, n_2) divided by the Planck constant hh: ν=ΔE(n1,n2)h\nu = \frac{\Delta E(n_1, n_2)}{h} where ΔE(n1,n2)=En2−En1\Delta E(n_1, n_2) = E_{n_2} - E_{n_1} is the energy difference between the n2n_2-th and n1n_1-th Bohr levels.

theorem

ν(n2,n1)=−ν(n1,n2)\nu(n_2, n_1) = -\nu(n_1, n_2)

For any two natural numbers n1n_1 and n2n_2 representing energy levels of a hydrogen atom, let ν(n1,n2)\nu(n_1, n_2) denote the transition frequency. Exchanging the two levels changes the sign of the transition frequency: ν(n2,n1)=−ν(n1,n2)\nu(n_2, n_1) = -\nu(n_1, n_2)

theorem

The Transition Frequency of an Energy Level to Itself is 0

For any energy level index n∈Nn \in \mathbb{N}, the transition frequency ν\nu between the level nn and itself is 00.

abbrev

Rydberg frequency RνR_\nu

The Rydberg frequency RνR_\nu is the real number defined as the ratio of the Rydberg energy RyRy to the Planck constant hh: Rν=RyhR_\nu = \frac{Ry}{h} It represents the frequency of a photon whose energy is equal to the Rydberg energy.

definition

Transition wavelength λ=c/ν\lambda = c/\nu

For a given speed of light cc and two natural numbers n1n_1 and n2n_2 representing energy levels of a dd-dimensional hydrogen atom, the wavelength λ\lambda associated with the transition from level n2n_2 to level n1n_1 is defined as: λ=cν\lambda = \frac{c}{\nu} where ν\nu is the transition frequency between these levels. When n2>n1n_2 > n_1 (and assuming d≥2,k≠0d \ge 2, k \neq 0), λ\lambda represents the wavelength of the emitted photon. If n2<n1n_2 < n_1, the transition corresponds to absorption, and the resulting wavelength is negative, with its absolute value ∣λ∣|\lambda| representing the physical wavelength of the absorbed photon. For n1=n2n_1 = n_2, where the frequency is zero, the wavelength is defined as 00.

theorem

λ=c/ν\lambda = c / \nu

For any speed of light cc and natural numbers n1n_1 and n2n_2 representing indices of energy levels, the transition wavelength λ\lambda between these levels is given by the ratio of the speed of light to the transition frequency ν\nu: λ=cν\lambda = \frac{c}{\nu}

theorem

Rydberg Formula for Transition Energy En2−En1E_{n_2} - E_{n_1}

For any two natural numbers n1n_1 and n2n_2, the transition energy En2−En1E_{n_2} - E_{n_1} between the n2n_2-th and n1n_1-th Bohr energy levels of a dd-dimensional hydrogen atom is given by the Rydberg formula: En2−En1=Ry(1Ln12−1Ln22) E_{n_2} - E_{n_1} = Ry \left( \frac{1}{L_{n_1}^2} - \frac{1}{L_{n_2}^2} \right) where RyRy is the Rydberg energy and Ln=n+d−12L_n = n + \frac{d - 1}{2} is the level index (effective principal quantum number) for the nn-th level.

theorem

Rν=mk24πℏ3R_\nu = \frac{m k^2}{4 \pi \hbar^3}

The Rydberg frequency RνR_\nu is given by the expression: Rν=mk24πℏ3R_\nu = \frac{m k^2}{4 \pi \hbar^3} where mm is the mass of the particle, kk is the coupling constant of the potential, and ℏ\hbar is the reduced Planck constant.

theorem

Rν≥0R_\nu \ge 0

The Rydberg frequency RνR_\nu is non-negative, that is, Rν≥0R_\nu \ge 0.

theorem

k≠0  ⟹  Rν>0k \neq 0 \implies R_\nu > 0

If the potential parameter kk is non-zero (k≠0k \neq 0), then the Rydberg frequency RνR_\nu is strictly positive (Rν>0R_\nu > 0).

theorem

Rν=0R_\nu = 0 if k=0k = 0

If the potential parameter kk is equal to 00, then the Rydberg frequency RνR_\nu is equal to 00.

theorem

Rydberg formula for transition frequency ν=Rν(1Ln12−1Ln22)\nu = R_\nu \left( \frac{1}{L_{n_1}^2} - \frac{1}{L_{n_2}^2} \right)

For any natural numbers n1n_1 and n2n_2, the transition frequency ν\nu between the Bohr levels n2n_2 and n1n_1 is given by the Rydberg formula: ν=Rν(1Ln12−1Ln22)\nu = R_\nu \left( \frac{1}{L_{n_1}^2} - \frac{1}{L_{n_2}^2} \right) where RνR_\nu is the Rydberg frequency and Ln=n+d−12L_n = n + \frac{d - 1}{2} is the level index (effective principal quantum number) for the nn-th energy level in dd dimensions.

theorem

ν(n1,n2)>0\nu(n_1, n_2) > 0 for n1<n2n_1 < n_2

Consider a dd-dimensional hydrogen atom with potential parameter kk. If d≥2d \geq 2 and k≠0k \neq 0, then for any two energy level indices n1,n2∈Nn_1, n_2 \in \mathbb{N} such that n1<n2n_1 < n_2, the transition frequency ν(n1,n2)\nu(n_1, n_2) is strictly positive.

theorem

The transition frequency ν(n1,n2)\nu(n_1, n_2) is negative when n2<n1n_2 < n_1

For a dd-dimensional hydrogen atom with dimension d≥2d \ge 2 and potential constant k≠0k \neq 0, the transition frequency ν(n1,n2)\nu(n_1, n_2) between the levels with indices n1n_1 and n2n_2 is strictly negative if n2<n1n_2 < n_1. This corresponds to an upward transition (absorption of a photon) from level n2n_2 to level n1n_1.

theorem

Rydberg Formula for the Wavenumber 1/λ1/\lambda

For a given speed of light cc and two energy level indices n1,n2∈Nn_1, n_2 \in \mathbb{N} of a dd-dimensional hydrogen atom, the inverse of the transition wavelength λ\lambda (the wavenumber) is given by the Rydberg formula: 1λ=Rνc(1Ln12−1Ln22)\frac{1}{\lambda} = \frac{R_\nu}{c} \left( \frac{1}{L_{n_1}^2} - \frac{1}{L_{n_2}^2} \right) where RνR_\nu is the Rydberg frequency and LnL_n is the level index (effective principal quantum number) defined as Ln=n+d−12L_n = n + \frac{d-1}{2}.

theorem

For d≥2d \ge 2 and k≠0k \neq 0, ν(n1,n2)\nu(n_1, n_2) is strictly increasing in n2n_2

Consider a hydrogen atom in dimension d≥2d \ge 2 with potential parameter k≠0k \neq 0. For a fixed energy level index n1∈Nn_1 \in \mathbb{N}, the transition frequency ν(n1,n2)=En2−En1h\nu(n_1, n_2) = \frac{E_{n_2} - E_{n_1}}{h} is strictly increasing with respect to the level index n2n_2. That is, for any n2,n3∈Nn_2, n_3 \in \mathbb{N}, if n2<n3n_2 < n_3, then ν(n1,n2)<ν(n1,n3)\nu(n_1, n_2) < \nu(n_1, n_3).

theorem

Monotonicity of the Hydrogen Transition Frequency ν(n1,n2)\nu(n_1, n_2) with respect to n2n_2 for d≥2d \ge 2

Let dd be the dimension of a hydrogen atom such that d≥2d \ge 2. For a fixed lower energy level index n1∈Nn_1 \in \mathbb{N}, the transition frequency ν(n1,n2)\nu(n_1, n_2) is monotonically non-decreasing with respect to the upper energy level index n2∈Nn_2 \in \mathbb{N}. That is, for any n2,n3∈Nn_2, n_3 \in \mathbb{N}, if n2≤n3n_2 \le n_3, then ν(n1,n2)≤ν(n1,n3)\nu(n_1, n_2) \le \nu(n_1, n_3).

theorem

lim⁡n2→∞ν(n1,n2)=RνLn12\lim_{n_2 \to \infty} \nu(n_1, n_2) = \frac{R_\nu}{L_{n_1}^2}

For a fixed lower energy level n1∈Nn_1 \in \mathbb{N}, as the upper energy level n2n_2 tends to infinity, the transition frequency ν(n1,n2)\nu(n_1, n_2) converges to the series limit: lim⁡n2→∞ν(n1,n2)=RνLn12\lim_{n_2 \to \infty} \nu(n_1, n_2) = \frac{R_\nu}{L_{n_1}^2} where RνR_\nu is the Rydberg frequency and Ln1=n1+d−12L_{n_1} = n_1 + \frac{d-1}{2} is the effective principal quantum number (level index) for the level n1n_1 in dd dimensions.

abbrev

Lyman frequency νLyman(n)\nu_{\text{Lyman}}(n)

For a natural number nn, the Lyman frequency νLyman(n)\nu_{\text{Lyman}}(n) is defined as the frequency of a photon associated with the transition between the nn-th energy level and the ground state (level 00). It is calculated as the transition frequency from level 00 to level nn: νLyman(n)=ν(0,n)=En−E0h\nu_{\text{Lyman}}(n) = \nu(0, n) = \frac{E_n - E_0}{h} where EnE_n is the energy of the nn-th level and hh is the Planck constant.

abbrev

Balmer series frequency ν(n)\nu(n)

For a natural number nn, the Balmer frequency is defined as the frequency of the photon associated with the transition between the energy level of index nn and the energy level of index 11. It represents the nn-th line of the Balmer series for a dd-dimensional hydrogen atom, calculated as: ν=En−E1h\nu = \frac{E_n - E_1}{h} where EnE_n and E1E_1 are the Bohr energy levels and hh is Planck's constant.

abbrev

Paschen frequency for level nn

For a natural number nn representing an energy level, the Paschen frequency is the frequency of the photon involved in the transition between level nn and the level with index 2 in a dd-dimensional hydrogen atom. It is defined as: ν=En−E2h\nu = \frac{E_n - E_2}{h} where EnE_n and E2E_2 are the Bohr energy levels and hh is the Planck constant.

theorem

νBalmer<νLyman\nu_{\text{Balmer}} < \nu_{\text{Lyman}} for 2≤d≤52 \le d \le 5

In a dd-dimensional hydrogen atom model with 2≤d≤52 \leq d \leq 5 and a non-zero coupling constant kk, the frequency of any line in the Balmer series is strictly less than the frequency of any line in the Lyman series. Formally, for any n2∈Nn_2 \in \mathbb{N} and n3∈N+n_3 \in \mathbb{N}^+ (where n3>0n_3 > 0), the Balmer frequency νBalmer(n2)\nu_{\text{Balmer}}(n_2) and the Lyman frequency νLyman(n3)\nu_{\text{Lyman}}(n_3) satisfy the inequality: νBalmer(n2)<νLyman(n3)\nu_{\text{Balmer}}(n_2) < \nu_{\text{Lyman}}(n_3) where the frequencies are defined by the energy transitions νBalmer(n)=En−E1h\nu_{\text{Balmer}}(n) = \frac{E_n - E_1}{h} and νLyman(n)=En−E0h\nu_{\text{Lyman}}(n) = \frac{E_n - E_0}{h} between the Bohr levels En=−Ry/(n+d−12)2E_n = -Ry / (n + \frac{d-1}{2})^2. This separation of spectral series holds because for these dimensions, the Balmer series limit is less than or equal to the first Lyman line frequency.