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If a string being parsed as a character code is more than one character long, or starts with a non-digit, it is always looked up as a name in an encoding vector before being considered as a numeric code. We do this because you can always specify a particular value in one of the numeric formats, if that's what you want.
The encoding vector used varies with the program; you can always define an explicit encoding vector with the `-encoding' option. If you don't specify one explicitly, programs which must have an encoding vector use a default; programs which can proceed without one do not. See section 5.3 Encoding files, for more details on encoding vectors.
As a practical matter, the only character names which have length one are the 52 letters, `A'--`Z', `a'--`z'. In virtually all common cases, the encoding vector and the underlying character set both have these in their ASCII positions. (The exception is machines that use the EBCDIC encoding.)