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    HW#2

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    HW#2

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    HW#2

    Recall:
    The dipole operator is given by
    "

    𝜇̂ = $ 𝑞! (𝑥(! 𝒊 + 𝑦(! 𝒋 + 𝑧̂! 𝒌)


    !#$
    where 𝑥(! , 𝑦! , 𝑧̂! are the position operator, and 𝑞! is the charge of the ith particle; 𝒊, 𝒋, 𝒌 are the unit
    vector pointing x,y,z directions.

    Q1 (1 pt). For any 𝑁 × 𝑁 matrix 𝐴4 whose eigenvectors and eigenvalues are given by ℰ =
    {|𝑒$ ⟩, |𝑒% ⟩ ,… ,|𝑒" ⟩} and {𝜆$ , 𝜆% , … , 𝜆" }, show that the matrix 𝐴4 + 𝜆1? has the same eigenvectors.
    What are the corresponding eigenvalues?

    Q2 (2 pt).
    Using the Hamiltonian
    A = 𝜔𝑆4& .
    𝐻
    write the expectation values of 〈𝑆4' 〉(𝑡), 〈𝑆4( 〉(𝑡), 〈𝑆4& 〉(𝑡) as a function of time when the quantum
    state |𝜓, 𝑡⟩ is given by |+⟩ at 𝑡 = 0.

    Q3 (0.5+0.5 = 1 pt). Suppose that we have a set of uncountable “basis” {|𝑥⟩} where we can
    express any quantum eigenstate |𝑒) ⟩ of a given particle as
    *
    |𝑒) ⟩ = I 𝜓) (𝑥)|𝑥⟩𝑑𝑥
    +*
    where 𝑥(|𝑥⟩ = 𝑥|𝑥⟩.
    This is more or less “continuous” analog of our familiar linear combination |𝑎⟩ = ∑"
    )#$ 𝑐) |𝑒) ⟩.
    The coefficient 𝜓) (𝑥) is known as wave function.
    |𝑥⟩ satisfies the orthonormal condition
    ⟨𝑥′|𝑥⟩ = 𝛿(𝑥 − 𝑥 , )
    where 𝛿(𝑥) is a delta function.
    a) show that 𝜓(𝑥) satisfies
    *
    I 𝜓)∗ (𝑥)𝜓. (𝑥)𝑑𝑥 = 𝛿).
    +*
    b) If 𝜓) (𝑥) is either even or odd (for spherical system, even and odd are called gerade and
    ungerade, respectively) function of 𝑥, show that
    ⟨𝑒) |𝑥(|𝑒) ⟩ = 0

    Q4 (1 pt). The concept of wavefunction can be extended to three-dimensional.


    For example,
    * * *
    |𝑒) ⟩ = I I I 𝜓) (𝑥, 𝑦, 𝑧)|𝑥, 𝑦, 𝑧⟩ 𝑑𝑥𝑑𝑦𝑑𝑧
    +* +* +*
    where (𝑥, 𝑦, 𝑧) is the cartesian coordinate of a particle.
    |𝑥, 𝑦, 𝑧⟩ satisfies
    𝑥(|𝑥, 𝑦, 𝑧⟩ = 𝑥|𝑥, 𝑦, 𝑧⟩
    𝑦(|𝑥, 𝑦, 𝑧⟩ = 𝑦|𝑥, 𝑦, 𝑧⟩
    𝑧̂|𝑥, 𝑦, 𝑧⟩ = 𝑧|𝑥, 𝑦, 𝑧⟩

    Using the property of a wave function of a p-orbital in Hydrogen atom, evaluate ⟨𝑝& |𝑧̂ |𝑝& ⟩.

    Q5 (2 pt). Provided the differential equations given by


    𝑑
    T〈𝐼4 (𝑡)〉 − 〈𝐼4/0 〉V = −𝑅1 T〈𝐼4& (𝑡)〉 − 〈𝐼4/0 〉V − 𝑅12 T〈𝑆4& (𝑡)〉 − 〈𝑆4/0 〉V
    𝑑𝑡 &
    𝑑
    T〈𝑆4 (𝑡)〉 − 〈𝑆4/0 〉V = −𝑅2 T〈𝑆4& (𝑡)〉 − 〈𝑆4/0 〉V − 𝑅12 T〈𝐼4& (𝑡)〉 − 〈𝐼4/0 〉V
    𝑑𝑡 &

    where 〈𝐼4/0 〉, 〈𝑆4/0 〉, 𝑅1 , 𝑅2 and 𝑅12 are some positive constants and the initial conditions are given
    by
    〈𝐼4& (0)〉 = 𝑀1 cos(𝜔1 𝑡$ )
    〈𝑆4& (0)〉 = 𝑀2 cos(𝜔2 𝑡$ )

    solve for 〈𝐼4& (𝑡)〉 and 〈𝑆4& (𝑡)〉.

    Q6 (1pt) If the rate of excitation is given by 𝑘/' , derive the expression for the rate of the
    stimulated emission 𝑘/. .

    Q7 (0.5+0.5+0.5=1.5pt) Consider a formaldehyde shown in Figure 1.


    Let ]^2𝑝&,4 `, ^2𝑝&,5 `a corresponds to an electron in the quantum state described by the atomic p-
    orbital of carbon and oxygen, respectively.
    If the molecular orbital of a formaldehyde is given by
    |𝜋⟩ = ^2𝑝&,4 ` + ^2𝑝&,5 `
    and its excited state is given by
    |𝜋 ∗ ⟩ = ^2𝑝&,4 ` − ^2𝑝&,5 `
    Let the electric dipole operator of the formaldehyde be 𝜇̂ = 𝜇̂ ' 𝒊 + 𝜇̂ ( 𝒋 + 𝜇̂ & 𝒌. (𝒊, 𝒋, 𝒌 are unit
    vector pointing to x,y and z diretions)
    TRUE or FALSE
    (a) ⟨𝜋|𝜇̂ ' |𝜋 ∗ ⟩ can be nonzero.
    (b) ⟨𝜋|𝜇̂ ( |𝜋 ∗ ⟩ is zero.
    (c) ⟨𝜋|𝜇̂ & |𝜋 ∗ ⟩ is zero

    Figure 1
    Q8 (1+1.5=2.5 pt) Suppose the absorption spectrum of acetaldehyde has gaussian shape.
    Calculate the oscillator strengths of the following transitions: 𝑛 → 𝜋 ∗ (𝜆678 ≃ 2900 ), 𝜖678 ≃
    15 𝑀+$ cm+$ , ∆𝜔! ≃ 500 cm+$ and 𝜋 → 𝜋 ∗ (𝜆678 ≃ 1816 ), 𝜖678 ≃ 109 𝑀+$ cm+$ , ∆𝜔! ≃
    " "
    1500 cm+$
    Recall that 𝜖 is called molar extinction coefficient.
    In addition, find the theoretical average lifetime of the spontaneous emission from the Einstein
    equation for each transition (𝜋 ∗ → 𝑛 and 𝜋 ∗ → 𝜋).

    Q9 (1pt) If the rate of fluorescence is given by 𝑘: = 1 × 10; 𝑠 +$ , the rate of intersystem


    crossing is given by 𝑘124 = 1 × 10< 𝑠 +$ , the rate of internal conversion is 𝑘14 = 1 × 10= 𝑠 +$ ,
    and the rate of quenching 𝑘> = 1 × 10; 𝑀+$ 𝑠 +$ . What is the fluorescence quantum yield 𝜙:
    when the concentration of the quencher is [Q] = 10+? 𝑀?

    Q10 (2pt) Suppose the instrument which has the path length of 1 mm; incident light of irradiance
    𝐼@ = 100 𝑚𝑊 𝑚+% at 280 nm. If you have a protein A with the sequence
    MEAIAKHDFSATADDELSFRKTQILKILNMEDDSNWYRAELDGKEGLIPSNYIEMKSHK
    If the concentration of A is 10+< 𝑀, estimate the irradiance after passing through the cuvette.

    Q11 (1 pt bonus)
    If the 〈𝐼4& (𝑡)〉 and 〈𝑆4& (𝑡)〉 you found in Q5 is multiplied by cos(𝜔1 𝑡% ) and cos(𝜔2 𝑡% ), that is
    𝑎(𝑡$ , 𝑡% ) = 〈𝐼4& (𝑡)〉 cos(𝜔1 𝑡% ) + 〈𝑆4& (𝑡)〉 cos(𝜔2 𝑡% )
    Plot the Fourier transform of 𝐹 [𝑎(𝑡$ , 𝑡% )] = 𝑎(𝑣$ , 𝑣% ).

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