Yes, under Benford’s law
the expected frequency of a specific leading pair of digits
$ d_1d_2 $
$\big( = 10d_1 \! + d_2 = d $,
with $ d \in \{10,11,12,\ldots,99\} ~\big) $
is just as your program calculated.
\begin{align}
P ( \text {first two digits are} ~ d_1 d_2 )
& = P ( \text {first two digits are} ~ 10d_1 \! + d_2 ) \\[1ex]
& = P ( \text{first two digits are} ~ d ) \\[1ex]
& = \log_{10} \left( 1 + {1 \over d}\right)
\end{align}
Agreeing with your implicit conjecture,
this holds in general for $n$ leading digits
where $d = d_1 d_2 d_3 ... d_n$
with $d_1 \in \{ 1,2,3,...,9 \}$,
as gathered from
An Introduction to Benford's Law, Chapter 1,
Princeton University Press
(no author or year given) — stated
slightly differently here
in a subtractive format
that facilitates many applications.
\begin{align}
P ( \text {first} ~ n ~ \text{digits are} ~ d_1 d_2 d_3 ... d_n )
& = P ( \text{first} ~ \text{digits are} ~ d ) \\[1ex]
& = \log_{10} (d{+}1) - \log_{10} d
\kern 7.5em \end{align}
An example for the original question
gives the same result as the familiar format.
\begin{align}
P ( \text{first} ~ 2 ~ \text{digits are} ~ 76 )
& = \log_{10} 77 - \log_{10} 76 \\[1ex]
& = \log_{10} {\small { 77 \over 76 }} \\[1ex]
& = \log_{10} \left( 1 + { \small{ 1 \over 76 }} \right)
\kern 6em \end{align}
The subtractive format shows its flexibility
on other conceivable questions about the first two digits.
\begin{align}
P ( \text {first 2 digits are equal} )
& = P ( \text {first are 11} )
+ P ( \text{first are 22} )
+ \cdots
+ P ( \text{first are 99} ) \\[2ex]
& = ( \log_{10} 12 - \log_{10} 11 )
+ ( \log_{10} 23 - \log_{10} 22 ) \\[.5ex]
& \kern 12em + \cdots
+ ( \log_{10} 100 - \log_{10} 99 ) \\
& = \log_ {10} {\small{ 12 \cdot 23 \cdots 100 \over
11 \cdot 22 \cdots 99 }} \\[1.5ex]
& = 10.9 \%
\end{align}
\begin{align} \kern 3.5em \raise 2ex \strut
P ( \text {2nd digit is} ~ 6 )
& = P ( \text {first are 16} )
+ P ( \text{first are 26} )
+ \cdots
+ P ( \text{first are 96} ) \\[2ex]
& = ( \log_{10} 17 - \log_{10} 16 )
+ ( \log_{10} 27 - \log_{10} 26 ) \\[.5ex]
& \kern 12em + \cdots
+ ( \log_{10} 97 - \log_{10} 96 ) \\
& = \log_ {10} {\small{ 17 \cdot 27 \cdots 97 \over
16 \cdot 26 \cdots 96 }} \\[1.5ex]
& = 9.3 \%
\end{align}
This format also telescopes nicely when verified against
the most famous prediction of Benford’s law,
that 1 is the first significant digit
in approximately 30.1% of suitably random numbers.
The first 3 digits are employed this time for variety.
\begin{align} \kern 4.5em
P ( \text {first digit is} ~ 1 )
& = P ( \text {first are 199} )
+ P ( \text{first are 198} )
+ \cdots
+ P ( \text{first are 100} ) \\[2ex]
& = ( \log_{10} 200 - \log_{10} 199 )
+ ( \log_{10} 199 - \log_{10} 198 ) \\[.5ex]
& \kern 12em + \cdots
+ ( \log_{10} 101 - \log_{10} 100 ) \\
& = \log_{10} 200 - \log_{10} 100 \\[1.5ex]
& \equiv 30.1 \%
\end{align}
(The material above was learned while applying Benford’s law
to Roman numbers in
a puzzle.)